W2082: Evaluating the Physical and Biological Availability of Pesticides and Contaminants in Agricultural Ecosystems

(Multistate Research Project)

Status: Inactive/Terminating

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SAES-422 Reports

Annual/Termination Reports:

[04/05/2011] [03/01/2012] [04/08/2013]

Date of Annual Report: 04/05/2011

Report Information

Annual Meeting Dates: 01/05/2011 - 01/06/2011
Period the Report Covers: 10/01/2009 - 09/01/2010

Participants

University of California, Riverside, Jay Gan (represented by Lisa Delgado-Moreno); Colorado State University, Thomas Borch;Connecticut - Connecticut Agricultural Experiment Station-New Haven,Joseph J. Pignatello;Hawaii - University of Hawaii, Jon-Paul Bingham;Hawaii - University of Hawaii, Chitteranjan Ray;Illinois - University of Illinois,Mike Hirschi;Kentucky - University of Kentucky,Elisa M D'Angelo;Michigan - Michigan State University,Hui Li;Minnesota - University of Minnesota,Michael Sadowsky; Missouri - University of Missouri,Keith Goyne;North Dakota - North Dakota State University, Thomas DeSutter; Pennsylvania - Pennsylvania State,John E. Watson;Pennsylvania Cooperative Extension,Deno De Ciantis;Texas A&M, Kingsville,Shad D Nelson;USDA-ARS/Arizona, Clinton Williams;USDA-ARS/Minnesota,W. Koskinen; Lee Sommers, Administrative Advisor (Colorado State University)

Brief Summary of Minutes

Jack Watson served as Chair of the committee and Joe Pignatello served as Secretary. The Administrative Advisor, Lee Sommers, summarized the vision and roles of NIFA and discussed the AFRI grants program. It was determined by consensus of the attending members that next year's meeting would be hosted by Shad Nelson of Texas A&M, in Corpus Christie, in January 2012. Each participant provided a research update, with discussion following each presentation. Dr. Dick Green, a former member of W-82 stopped by to greet the attending members; a pleasant surprise.

Accomplishments

Objective 1: To identify and quantify fundamental chemical, physical, and biological processes relevant to pesticides and contaminants in agricultural ecosystems I. USDA-ARS - Arizona A. Influence of pKa Accomplishment/output: Contaminants such as antibiotics, found in treated effluent, have been identified as a potential problem for use of this water for irrigation due to the potential for development of antibiotic resistance. Initial environmental fate parameters were determined for lincomycin in soils. It was found that lincomycin sorption is related to soil pH. When soil pH is below 7.6 lincomycin is highly mobile, however, when soil pH is above 7.6 mobility was significantly reduced. These results can be used to determine site-specific guidelines for disposal and use of reclaimed water. B. Development of Antibiotic Resistance Accomplishment/output: Most wastewater treatment plants are not designed for the removal of residual antibiotics, which can be released into the environment with treated wastewater, increasing public health concerns for the potential for development of antibiotic resistance (AR) in soil bacteria. We are comparing levels of resistance to 16 antibiotics in soil bacteria isolated from water storage basins recharged with either reclaimed water or natural groundwater in central Arizona. Initial results suggest that resistance to multiple antibiotics, including tetracycline, daptomycin, and erythromycin, exists in both soils. Overall AR is not increased in soils exposed to reclaimed water. II. California - Riverside A. Bioavailability and phase partitioning: Accomplishment/output: 1. The effect of dissolved organic carbon (DOC) on pyrethroid sorption to sediment was essentially linear. Interactions between DOC and pyrethroids decreased sorption of some pyrethroids even further, implying that DOC-pyrethroid complexes were relatively stable in solution. DOC sources with higher contents of carboxylic and phenolic groups were found to have a higher potential to associate with pyrethroids. 2. We evaluated biodegradation of pyrene by Mycobacterium vanbaalenii PYR-1 as a function of sediment particle sizes. Analyses showed that the total organic carbon (TOC), black carbon (BC), and specific surface area (SSA) of the specific particle size fractions, instead of the particle size scale itself, were closely related with the mineralization rate. Subsequent model analysis showed that pyrene sorbed on silt and clay aggregates was directly utilized by the degrading bacteria. 3. Accurate measurement of adsorption coefficients for Polybrominated diphenyl ethers (PBDEs) using conventional batch methods can be confounded by biases caused by their sorption to dissolved organic carbon (DOC). Sorption isotherms were constructed for BDE-47 and BDE-99 in sediments by using different methods to measure the aqueous phase concentration Cw. This study showed that PBDE congeners have larger sorption coefficients than would be measured by the conventional method. B. Pesticide sorption and washoff on concrete: Accomplishment/output: We evaluated the dependence of washable pesticide residues on pesticide types, formulations, time exposed to outdoor conditions and number of washing cycles. Wash-off potential was consistently higher for solid formulations than for liquid formulations. Trace levels of pyrethroids were detected in the wash-off solution even after 14 washing-drying cycles over 42 d under outdoor conditions. We characterized sorption and desorption of permethrin, the most used pyrethroid insecticide. Sorption of 14C-permethrin to concrete was rapid, and the sorption isotherm was linear, with surface area-normalized Kd of 1.91 ± 0.1 mL/cm2. Permethrin became more resistant to desorption as the pesticide contact time on the concrete increased. When pesticide-treated concrete surfaces come in contact with runoff water, elevated concentrations may be expected initially, while the extended desorption implies a potential for sustained contamination. III. Minnesota USDA-ARS: Accomplishment/output: An enrichment culture approach was used to isolate a pure culture of the yeast Candida xestobii, which had the ability to use the herbicides metolachlor and alachlor as asole source of carbon for growth. LC-ESI-MS analyses indicated that C. xestobii degraded 60% of the added metolachlor after 4 d of growth, and converted up to 25% of the compound into CO2 after 10 days. A bacterium, Bacillus simplex, was also found to have the ability to catabolize metolachlor and use this herbicide as a sole source of carbon for growth. IV. Minnesota Univ of Mn A. Biodegradation and Mineralization Accomplishment/output: We examined 10 and 2 year histories of metolachlor and S-metolachlor applications, respectively, for microorganisms that had the ability to degrade this herbicide. Pure cultures of C. xestobii degraded 60% of the added metolachlor after 4 d of growth, and converted up to 25% of the compound into CO2 after 10 days. In contrast, pure cultures of B. simplex biodegraded 30% of metolachlor following 5 d of growth in minimal medium. Yeast degraded other acetanilide compounds and 80% of acetochlor and alachlor were degraded after 15 h and 41 h of growth, respectively. B. Bioavailability-Organoclay Formulations Accomplishment/output: Pesticide formulations based on organoclays have been proposed to prolong the efficacy and reduce the environmental impact of pesticides in soil. This research addressed the question of whether atrazine in organoclay-based formulations is irreversibly sorbed or is bioavailable for bacterial degradation in soil. Bound residues increased from <4% at day 0 to ~17% after the 2 week incubation for both the formulated and free forms of atrazine. C. X-Ray structure and mutational analysis of TrzN. Accomplishment/output: Atrazine chlorohydrolase, TrzN, initiates bacterial metabolism of the herbicide atrazine by hydrolytic displacement of a chlorine substituent from the s-triazine ring. The present study describes crystal structures and reactivity of wild-type and active site TrzN mutant enzymes. The structure and kinetics are reminiscent of carbonic anhydrase that uses a threonine to assist in positioning water for reaction with carbon dioxide.Both structure and kinetic determinations suggest that the E241 side chain provides a proton to N-1 of the s-triazine substrate to facilitate nucleophilic displacement at the adjacent C-2. D. Bacterial Ammeline Metabolism Accomplishment/output: Melamine toxicity in mammals is due to the blockage of kidney tubules by insoluble complexes of melamine with cyanuric acid or uric acid. Bacteria metabolize melamine via three consecutive deamination reactions to generate cyanuric acid. The second deamination reaction, in which ammeline is the substrate, is common to many bacteria, but the genes and enzymes responsible have not been previously identified. In this study we used a combination of bioinformatics and experimental data to identify guanine deaminase as the enzyme responsible for this biotransformation. V. Missouri Veterinary Antibiotic Sorption Accomplishment/output: The potential of veterinary antibiotics (VAs) to impact human and environmental health requires the development and evaluation of land management practices that mitigate VA loss from manure-treated agroecosystems. Vegetative buffer strips (VBS) are postulated to be one management tool that can reduce VA transport to surface water resources. Oxytetracycline (OTC) was strongly adsorbed by all soils considered (agroforestry buffer, grass buffer, and cropland soil) and was not readily extractable. OTC and sulfadimethoxine (SDT) solid to solution partition coefficients are significantly greater for soils planted to VBS relative to grain crops. Significant differences in OTC and SDT Kd values were also noted among the soil series studied. Clay content and pH were the most important soil properties controlling OTC and SDT adsorption, respectively. Agroforestry and grass buffer strips may effectively mitigate antibiotic loss. VI. Kentucky A. Livestock antibiotics Accomplishment/output: Experiments were undertaken to determine the level at which three antibiotics would have adverse effects on selected indicators. Changes in NO3- and NO2-, N2O gas, and fatty acid methyl ester (FAME) levels in soils were measured to assess antibiotic affects on nitrification, denitrification, and microbial community structure, respectively. Bacitracin did not inhibit nitrification in the soils at any concentration up to 500 mg/kg compared to the zero level control. Roxarsone inhibited nitrification at >150 mg/kg in the shoulder and back slope positions and at 500 mg/kg at all the positions, but not at lower concentrations. Virginiamycin inhibited nitrification at >5 mg/kg in the shoulder, >15 mg/kg at backslope and >50 mg/kg at all positions. Bacitracin inhibited denitrification at 500 mg/kg soil, however, virginiamycin and roxarsone did not inhibit denitrification any concentration up to 500 mg/kg. Bacitracin did not affect any of the 60 FAMEs compared to the zero level control. Roxarsone and virginiamycin at 1 mg/kg also did not affect any of the FAMES. Roxarsone at 100 mg/kg increased two monounsaturated FAMEs and decreased one monounsaturated FAME, and virginiamycin at 100 mg/kg increased two monounsaturated FAMES and decreased branched monounsaturated FAME and polyunsaturated FAME 26:0. B. Sorption and resistance Accomplishment/output: Batch equilibrium sorption experiments were conducted to determine the extent that soils retained bacitracin, roxarsone, and virginiamycin in the concentration range 0-1500 mg/kg soil. Results showed that soils most strongly retained bacitracin followed by virginiamycin and roxarsone. To determine whether native soil microorganisms were resistant to antibiotics, microbes were extracted from soil, exposed to increasing levels of antibiotics in liquid culture media, and evaluated for growth from changes in turbidity in culture tubes over three days. Results showed that microbial growth was high and not affected at concentrations up to 100 mg/L solution compared to zero level control. VII. Colorado A. Transport Accomplishment/output: A field-scale study was conducted to assess the potential for runoff of seventeen different hormones, including androgens, estrogens, and progestogens from an agricultural field applied with biosolids and the major mechanisms controlling hormone transport during simulated rainfall events. Whole water runoff samples prior to biosolids application had low concentrations of a few hormones. In contrast, significantly higher concentrations of multiple estrogens, androgens, and progesterone were observed in runoff samples taken 1, 8 and 35 days after biosolids application. Androgen runoff concentrations declined from day 1 to day 35 after biosolids application but the concentrations, in particular for androstenedione, observed 35 days after biosolids application were still higher than concentrations known to affect the endocrine system of aquatic organisms. A significant positive correlation was observed between rainfall amount and hormone mass fluxes. Hormones in runoff were primarily present in the aqueous phase. B. Biodegradation Accomplishment/output: The potential for biodegradation of testosterone, 17²-estradiol (E2) and progesterone by swine (Sus scrofa) manure-borne bacteria was examined. The impact of temperature, pH (6, 7, and 7.5), glucose amendments (0, 3, and 22 mmol L1), and presence of oxygen on testosterone degradation kinetics was determined. Testosterone, 17²-estradiol and progesterone were biodegraded within 25 h of reaction initiation under aerobic conditions. The half-life (t1/2) for the degradation of testosterone under anaerobic conditions was six times longer than aerobic conditions. Testosterone degradation was found to significantly increase when incubated at 37°C vs. 22°C. The impact of pH and glucose amendments on the testosterone degradation rate were found to be small. Six DNA sequences of bacteria from the Proteobacteria phylum widely distributed among six different genera - Acinetobacter, Brevundimonas, Comamonas, Sphingomonas, Stenotrophomonas, and Rhodobacter were identified in a testosterone-degrading enriched culture. Six degradation products of testosterone were identified. One important observation in this study is that more than 48% of the 14C-testosterone had been mineralized to 14CO2 within 8 d of incubation. The high percentage of 14C-testosterone converted to 14CO2 suggests that testosterone served as an energy source. VIII. Michigan A. Environmental Pharmaceuticals Accomplishment/output: We investigated the occurrence and fate of four commonly used veterinary pharmaceuticals (amprolium, carbadox, monensin and tylosin) in an animal farm in Michigan. Amprolium and monensin were frequently detected in nearby surface waters, whereas tylosin or carbadox was rarely found. These pharmaceuticals were more frequently detected in surface runoff during the non-growing season than during the growing season. Pharmaceuticals resulting from post-harvest manure application appeared to be more persistent than those from spring application. High concentrations of pharmaceuticals in soils were generally observed in the sites where the respective concentrations in water were also high. Results suggest that soil is a sink for veterinary pharmaceuticals that can be disseminated to nearby surface waters. An analytical method was developed to quantitatively determine pharmaceuticals in biosolid (treated sewage sludge) from wastewater treatment plants (WWTPs). For the fifteen target pharmaceuticals commonly found in the environment, the overall method recoveries ranged from 49% to 68% for tetracyclines, 64% to 95% for sulfonamides, and 77% to 88% for other pharmaceuticals. The developed method was successfully validated and applied to the biosolid samples collected from WWTPs located in six cities in Michigan. Among the fifteen target pharmaceuticals, fourteen pharmaceuticals were detected in the collected biosolid samples. B. Sorption and Transformation Accomplishment/output: Cation exchange was the primary mechanism responsible for lincomycin sorption by soil clay minerals. The presence of Ca2+ in solution diminished lincomycin sorption. Clay interlayer hydration status strongly influenced lincomycin adsorption. Strongly hydrated exchangeable cations resulted in a more hydrated clay interlayer environment reducing sorption in the order of Ca- < K- < Cs-smectite. X-ray diffraction revealed that lincomycin was intercalated in smectite clay interlayers. Sorption capacity was limited by clay surface area rather than by cation exchange capacity. MnO2 caused rapid and extensive oxidative decomposition of clindamycin and lincomycin in aqueous solution. The presence of electrolyte and dissolved organic matter in aqueous solution, and increase of solution pH, diminished lincosamide binding to MnO2. Smectites, especially Cs-saponite, effectively adsorbed dibenzo-p-dioxin (DD) from water. Adsorption was promoted by exchangeable cations with low hydration energies, and negative charge in the smectite arising from the tetrahedral siloxane sheets. X-ray diffraction measurements revealed that as DD loading increased to e 8,000 mg/kg the clay basal spacing increased abruptly from 12.3 to 15.2 Å demonstrating DD intercalation. The 12.3 Å spacing provides an interlayer distance that closely matches the molecular thickness of DD. Fourier transformation infrared measurements confirm that adsorbed DD is present in orientations that are not parallel with the interlayer planar siloxane surfaces of smectite. C. Remediation Accomplishment/output: A novel method was developed for synthesizing subnano-sized zero-valent iron (ZVI) using smectite clay layers as templates. The clay-templated ZVI showed superior reactivity and efficiency compared to other previously reported forms of ZVI as indicated by the reduction of nitrobenzene; structural Fe within the aluminosilicate layers was nonreactive. This new form of subnano-scale ZVI may find utility in the development of remediation technologies for persistent environmental contaminants. Clay minerals were employed as template-supporting matrices to synthesize nano-scaled ZVI. The reactivity of the ZVI was evaluated based on the rate and extent of reduction of nitrobenzene to aniline. The results revealed that the reactivity of ZVI decreased with increasing particle sizes, and the ZVI intercalated in smectite clay manifested the highest reactivity. The reaction efficiency of the ZVI associated with smectite clay was estimated to be as high as 90%. IX. South Dakota A. Tylosin and chlortetracycline Accomplishment/output: Veterinary pharmaceuticals are commonly administered to animals for disease control and added into feeds at subtherapeutic level to improve feeding efficiency and are excreted in manure. The effects of these compounds on swine manure digestion in the presence and absence of the biocide sodium azide were studied. CTC enhanced initial hydrolysis reactions through volatile suspended solids productions, while inhibiting methane and carbon dioxide production. Tylosin did not affect methane and carbon dioxide production; however, the relative abundance of both hydrogen utilizing and acetate-only utilizing microbial populations were compromised. Sodium azide in the absence of antibiotics enhanced metabolic output and initial biomass productions, and this suggests that populations of Methanobacteriales and Methanosaetaceae spp. appeared to contain sufficient periplasmic bound reductase to effectively utilize acetate and hydrogen in the presence of sodium azide. B. GC-Clamp primer batches Accomplishment/output: Fingerprinting methods such as denaturing gradient gel electrophoresis (DGGE) have become a popular tool for the analysis of microbial communities. Three repeat syntheses of the same GC clamp primer, and two different GC clamp primers directed at the V3-5 region of the 16S rRNA gene were compared. Genomic DNA of two separate soil bacterial communities, and three bacterial species were amplified and resolved by DGGE. The DGGE profiles obtained with repeat-synthesized primers differed among each other as much as with alternate primers, for both soil DNA and pure single species. The GC clamp portion of members of amplicon pools varied among each other, deviating from the design sequence. C. Influence of chlortetracycline (CTC) Accomplishment/output: CTC is not sorbed or degraded in animals and is excreted in a bioactive form. Therefore, CTC may enter the environment through land-spreading of manure. This study determined the influence of a single application of manure with or without CTC on field soil microbial community characteristics. Manures from swine fed unamended or CTC-amended rations were applied to a soil that had no previous manure application history. Soil samples were analyzed for aerobic culturable counts on R2A agar and most probable number using 2,4-D as a sole carbon source. Soil extracts at 1, 7, and 42 d after application were subjected to denaturing gradient gel electrophoresis analysis of the V3 region of the 16S rRNA gene pool. Gels were analyzed using Neighbor Joining based on Euclidean distance and Raup-Crick multivariate statistical analyses and selected bands were extracted to identify predominant community members. X. Hawaii Transport of Cryptosporidum parvum oocysts Accomplishment/output: In order to gain more information about the fate of Cryptosporidium parvum oocysts in tropical volcanic soils, the transport and attachment behaviors of oocysts and oocyst-sized polystyrene microspheres were studied in the presence of two soils of differing chemical and physical properties. A third agricultural soil from Illinois was included for reference. Although a high (99%) removal of oocysts and microsphere within a volcanic ash soil occurred initially, transport was merely retarded because of highly reversible interactions with grain surfaces. This suggests contaminated volcanic ash soil could serve as a reservoir for subsequent contamination of groundwater. Because of the highly reversible nature of organic colloid immobilization in this soil type, C. parvum could contaminate surface water should overland flow pick up near-surface grains to which they are attached. XII. New Jersey Sorption and Redox Reactions Accomplishment/output: (1) The sorption of testosterone and androstenedione was nonlinear, and the log KOC values for testosterone and androstenedione are higher at lower aqueous phase concentrations. (2) For the three pesticides, atrazine, metolachlor and napropamide, humic acids (HA) and base extracted soil (BE), and particulate organic matter (POM) of the demineralized BE were used as sorbents. The herbicides sorption isotherms were nonlinear for the BE and POM, but relatively linear for HA. The isolated POM was an exceptionally good sorbent for the herbicides, and played a more important role than HA in the sorption of herbicides. Its sorption capacity was diminished in the bulk soil. (3) The measured KD values of tylosin fell into a narrow range between 1.7 and 12 L kg-1 for all the soils. The KD values appeared to correlate well with soil pH, but correlate poorly with the soil organic carbon content. Soil pH appeared to have strong influence on the sorption as tylosin is mainly positively charged at pH < 7.1. (4) Transformation of PCP and BPA by manganese dioxide (MnO2) was examined at different aquatic conditions. Transformation rates of lindane, pentachlorophenol (PCP) and bisphenol A (BPA) were found to be near first order with respect to the pollutant concentration, [MnO2] and [H+], respectively. Background divalent electrolytes considerably decreased the reaction. Dimers were detected as products for both systems. (5). Transformations of alpha-, beta-, and gama-hexachlorocyclohexanes (HCHs) were examined. In the absence of FeS, highly pH- and temperature-dependent reaction rates were observed for alpha- and gama-HCH, and pentachlorocyclohexene (PCCH) and 1,2,4- and 1,2,3- trichlorobenzene (TCB) were detected as the intermediate and final products of the transformation of both alpha- and gama-HCH. The calculated activation energies (Ea) at pH 9.26 were 60.4 ± 7.8 and 67.7 ± 8.7 kJ mol-1, respectively, for alpha- and gama-HCH. In the presence of FeS, transformation rates were dramatically enhanced, and both alpha- and gama-HCH isomers were degraded with petachlorocyclohexene (PCCH) and tetrachlorocyclohexene (TeCCH) as their respective intermediate products. Trichlorobenzenes (TCBs), dichlorobenzenes (DCBs), and chlorobenzene (CB) were detected as the final products for both HCH isomers. XIII. Connecticut A. Sulfamethazine Adsorption Accomplishments/Output: We studied the adsorption of the heavily used swine antibiotic sulfamethazine (SMZ) to a range of biochars. The ability of biochar to increase the apparent solids-water distribution coefficient of SMZ when added to soil was significant and trended with the biochar specific surface area. Adsorption by the most effective biochar was studied in detail in the absence of soil. The isotherm at pH 5 was highly nonlinear and gave Kd values that ranged from ~ 104 to 101 times greater than literature KOC values for SMZ. Sorption was greatest at about pH 5 where SMZ0 predominates; however, sorption at pH values where SMZ+ and SMZ- predominate was far greater than predicted by their respective Kow. Competition experiments indicated that sorption was driven primarily by nonspecific effects. B. Phenolic Acids Adsorption Accomplishments/Output: Depending on biomass source material and formation conditions black carbon (biochar) can be a strong adsorbent of organic compounds. Aromatic and phenolic carboxylic acid compounds exuded by plant roots play important roles in soil biology and allelopathy, and carboxylate functional groups are abundant in soil organic matter. We studied the adsorption of cinnamic and coumaric acids to different commercial biochar prototypes at pH above 6.9 where the acids are >99% dissociated. Isotherms were highly nonlinear, and give biochar-water distribution ratios up to 104 L/kg. Adsorption intensity trended with surface area and generally followed the order coumarate > cinnamate. Isotherms in unbuffered biochar-water mixtures became progressively suppressed relative to isotherms in buffered mixtures as equilibrium solute concentration increased. C. Cross-linking of Humic Acid with Organic Cross-linkers. Accomplishments/Output: The formation of intermolecular links between humic molecules and between strands within a humic molecule is referred to as cross-linking. Crosslinking increases molecular weight, lowers solubility, inhibits biodegradation, reduces molecular flexing within the organic solid phase, and influences the sorbent properties of organic matter. Two different organic cross-linking agents were used to cross-link a soil humic acid (HA). For diepoxide, the FTIR spectra showed the disappearance of the epoxy bands and the appearance of persistent bands associated with the aliphatic and C=O bands of the cyclohexyl groups. For 1,2,3,4-butanetetracarboxylic acid (BTCA), FTIR spectra showed bands signifying, i) the transient appearance of expected cyclic anhydride intermediates, ii) the disappearance of NaH2PO2, and iii) enhancement of C=O signal corresponding to incorporated BTCA group. In water buffered at pH 6 the solubility of both the DE- and BTCA-crosslinked HA was far lower than the solubility of HA itself, signifying extensive cross-linking. XIV. Pennsylvania Outputs: Sample cleanup and concentration procedures were worked out for soil samples such that we have confidence in results. . Experiments were conducted to determine the distribution of carbamazepine though the top 120 cm of forested, grassed and cropped lands. Results indicated that the amount of soil water contained in this depth was approximately equal to one years worth of irrigation, while the amount of carbamazepine was equivalent to approximately 15 years of application. In addition, the distribution of carbamazepine was concentrated near the soil surface, consistent with its strong sorption to organic carbon. Likely due to its high organic carbon content, forested lands had the highest concentration of carbamazepine. Approximately a 5% - 10% signal degradation occurs when antimicrobials are added to standards. This represents an important consideration in conducting analyses of soil extracts preserved with antimicrobials. XV. California Berkley Outputs: Analysis of the As speciation of the batch cultures in conjunction with the time-course of each abiotic treatment provided temporal information about which As species are formed in marine algae. Our data reveal edge effects of As uptake with enhanced As uptake as a function of P concentration. Arsenic hot spots were observed in cross-sectioned samples. Calcium also appears to be positively correlated with increased P concentration toward the edge of the disc. Objective 2: Integrate chemical and biological process information for use in models applicable across different spatial and temporal scales. I. Hawaii A. Transport Accomplishment/output: Experiments were conducted to examine the leachability of two estrogen hormones (17-beta estradiol [E2] and estrone [E1]) through small packed columns of three soils from Oahu, Hawaii. Both saturated and unsatured flow and transport experiments were conducted. Early arrival of E1 and E2 were observed in cinder compared to the Oxisol or the Mollisol. Both compounds showed enhanced transport in presence of lagoon effluent. E1 concentration in the column effluent was lower in saturated conditions than under unsaturated conditions. Also, batch sorption experiments were conducted for these two chemicals with and without microbial inhibitors (e.g., sodium azide) along with an antibiotic (chloramphenicol) and irradiation of the soil. Equilibrium was not achieved in 7 days in any of the soils for E2 alone or E1 and E2 combined. Microbial inhibition, including soil radiation did not completely remove this problem. B. Leaching and Runoff Accomplishment/output: Hawaii studied the behavior of the termiticide fipronil in Hawaii soils to assess its potential to contaminate ground and surface water. They characterized (1) adsorption, (2) transport, and (3) degradation. The concentration of fipronil in the leachate from the three soils correlated inversely with soil organic carbon content. Fipronil showed large losses through leaching, but small losses via runoff due to low volumes of runoff water generated and/or negligible particle-facilitated transport of fipronil. The half-life values of fipronil in all three soils were similar. Objective 3. Provide stakeholders with tools for developing strategies to ensure sustainable agriculture and to protect natural resource systems. I. Hawaii Registration of New Chemicals Accomplishment/output: Hawaii used data from studies to evaluate leaching, potential loss to runoff water, and ecotoxicological impacts, and provides that data to the state regulatory agency for action. If the compound appears to have significant impact to the local environment, it may be registered as a restricted use compound or the state requires that a certified applicator be responsible for its use. In that way, the state keeps track of the amount used and the locations treated.

Publications

Trigo, C., W.C. Koskinen, C. Rafael, M.J. Sadowsky, M.C. Hermosin, and J. Cornejo. 2010. Bioavailability of Organoclay Formulations of Atrazine in Soil. J. Agric. Food Chem., 2010, 58 (22), pp 1185711863. Munoz, A., W. C. Koskinen, L. Cox, and M. J. Sadowsky. 2011. Degradation of the herbicides metolachlor and alachlor by Candida xestobii. J. Agric. Food Chem. 58: (in press). Koskinen, W. C. and H. H. Cheng. 2011. Effects of Aging on Bioreactive Chemical Retention, Transformation, and Transport in Soil. J. Soils Sed. (in press) Williams, C.F., T.A. Coffelt and J.E. Watson. 2009. Increased soil sorption of Pendimethalin due to deposition of guayule-derived detritus. Soil Sci. Soc. Am. J. 73:1952-1957. Walker, C.W. and J.E. Watson. 2010. Adsorption of estrogens on laboratory materials and filters during sample preparation. J. Envir. Qual. 39:744-748. Jiang, W., K. Lin, D. Haver, S. Qin, F. Spurlock, and J. Gan. 2010. Wash-off potential of urban use insecticides on concrete surfaces. Environmental Toxicology and Chemistry 29: 1203-1208. Nillos, M.G., S.J. Qin, C. Larive, D. Schlenk, and J. Gan. 2009. Epimerization of cypermethrin stereoisomers in alcohols. Journal of Agricultural & Food Chemistry 57: 6938-6943. Nillos, M.G., J. Gan, and D. Schlenk. 2010. Chirality of organophophorus pesticides: Analysis and toxicity. Journal of Chromatography B 878:1277-1284. Han, A.L., Y. Ling, Z. Li, H.Y. Wang, Y. Wang, Q.F. Ye, L. Lu, and J. Gan. Plant availability and phytotoxicity of soil bound residues of herbicide ZJ0273, a novel acetolactate synthase potential inhibitor. Chemosphere 77: 955-961. Wang, H.Z., J.M. Xu, S.R. Yates, J.B. Zhang, J. Gan, J.C. Ma, J.J. Wu, and R.C. Xuan. 2010. Mineralization of metsulfuron-methyl in Chinese paddy soils. Chemosphere 78: 335-341. Wang, H.L., K.D. Lin, Z.A. Hou, B. Richardson, and J. Gan. 2010. Sorption of the herbicide terbuthylazine in two New Zealand forest soils amended with biosolids and biochars. Journal of Soils and Sediments 10: 283-289. Wang, W., Q.F. Ye, W. Ding, A.L. Han, H.Y. Wang, L. Lu, and J. Gan. 2010. Influence of soil factors on the dissipation of a new pyrimidynyloxybenzoic herbicide ZJ0273. Journal of Agricultural and Food Chemistry 58: 3062-3067. Zhao, M.R., F. Chen, C. Wang, Q. Zhang, J. Gan, and W.P. Liu. 2010. Integrative assessment of enantioselectivity in endocrine disruption and immunotoxicity of synthetic pyrethroids. Environmental Pollution 158: 19681973. Cui, X.Y., W. Hunter, Y. Yang, Y.X. Chen, and J. Gan. 2010. Bioavailability of sorbed phenanthrene and permethrin in sediments to Chironomus tentans. Aquatic Toxicology 98: 8390. Greenberg, L., M.K. Rust, J.H. Klotz, D. Haver, J.N. Kabashima, S. Bondarenko and J. Gan. 2010. Impact of ant control technologies on insecticide runoff and efficacy. Pest Management Science 66: 980-986. Lao, W.J., and J. Gan. Characterization of warfarin unusual peak profiles on oligoproline chiral high performance liquid chromatography columns. Journal of Chromatography A. 1217: 6545-6554. Nillos, M.G., S. Chajkowski, J.R. Rimoldi, J. Gan, R. Lavado, and D. Schlenk. 2010. Stereoselective biotransformation of permethrin to estrogenic metabolites in fish. Chemical Research in Toxicology 23: 1568-1575. Zhang, H.H., K.D. Lin, H.L. Wang, and J. Gan. 2010. Effect of Pinus radiata derived biochars on soil sorption and desorption of phenanthrene. Environmental Pollution 158: 2821-2825. OGeen, A.T., R. Budd, J. Gan, J.J. Maynard, S.J. Parikh, and R.A. Dahlgren. 2010. Mitigating non-point source pollution in agriculture with constructed and restored wetlands. Advances in Agronomy 108: 1-76. Delgao-Moreno, L., L. Wu, and J. Gan. 2010. Effect of dissolved organic carbon on sorption of pyrethroids to sediments. Environmental Science & Technology 44: 8473-8478. Lao, W.J., and J. Gan. 2010. Temperature effects on a doubly tethered diproline chiral stationary phase: Hold-up volume, enantioselectivity and robustness. Journal of Separation Science 33: 3052-3059. Wang, W., L. Moreno, Q.F. Ye, and J. Gan. 2011. Improved measurements of partition coefficients for polybrominated diphenyl ethers (PBDEs). Environmental Science & Technology (in press). Jiang, W., J. Gan, and D. Haver. 2011. Sorption and desorption of pyrethroid insecticide permethrin on concrete. Environmental Science & Technology (in press). Liu, W.P., H.H. Zhang, B.P. Cao, K.D. Lin, and J. Gan. Oxidative removal of bisphenol A using zero valent aluminum-acid system. Water Research (in press). Cui, X.Y., W. Hunter, Y. Yang, Y.X. Chen, and J. Gan. Biodegradation of pyrene in sand, silt and clay fractions of sediment. Biodegradation (in press). Zhang Q.; Yang, C.; Dang, Z.; Huang, W. (2011) Sorption of Tylosin on Agricultural Soils. Soil Science (in revision) Gao, N.; Yu, Z.; Hong, J.; Peng, P.; Huang, W. 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Hermosin, and J. Cornejo. 2010. Bioavailability of organoclay formulations of atrazine in soil. J. Ag. Food Chem. 58:11857-11863. Seffernick, J. L, E. Reynolds, A. A. Fedorov, E. Fedorov, S. Almo, M. J. Sadowsky, and L. P. Wackett. 2010. X-ray structure and mutational analysis of the atrazine chlorohydrolase TrzN. J. Biol. Chem.. 285: 3060630614. Seffernick, J.L., A.G. Dodge, M.J. Sadowsky, J.A. Bumpus, and L.P. Wackett. 2010. Bacterial ammeline metabolism by guanine deaminase. J. Bacteriol. 192:1106-1112. Munoz, Ana, W. Koskinen, L. Cox, and M. J. Sadowsky. 2010. Biodegradation and mineralization of metolachlor and alachlor by Candida xestobii. J. Ag. Food Chem. In Press. Chu, B., K.W. Goyne, S.H. Anderson, C.H. Lin, and R.P. Udawatta. 2010. Veterinary antibiotic sorption to agroforestry buffer, grass buffer, and cropland soils. Agroforest. Syst. 79: 67 80. Lin, C.-H., K.W. Goyne, R.J. Kremer, R.N. Lerch, and H.E. Garrett. 2010. Dissipation of sulfamethazine and tetracycline in the root zone of grass and tree species. J. Environ. Qual. 39: 1269 1278. Wu, S.-H, K.W. Goyne, R.N. Lerch, and C.-H. Lin. (In Press) Adsorption of isoxaflutole degradates to aluminum and iron hydrous oxides. J. Environ. Qual. Lin, C.-H., R.N. Lerch, K.W. Goyne, and H.E. Garrett. (Submitted). Reducing herbicide and veterinary antibiotic losses from agroecosystems using vegetative buffers. J. Environ. Qual. Banerjee, S. Effects of three livestock antibiotics on nitrification, denitrification, and microbial community structure in soils along a topographic gradient. Thesis. University of Kentucky. 2010. DAngelo, E.M. and A. Nunez. 2010. Effect of environmental conditions on polychlorinated biphenyl transformations and bacterial communities in a river sediment. Journal of Soils and Sediments 10: 1186-1199. Yang, Y-Y. Degradation and Transport Pathways of Steroid Hormones from Animal and Human Waste. Dissertation. Colorado State University, 2010. Blotevogel, J. Quantum Chemical Modeling of Redox Reactivity, Degradation Pathways and Persistence for Aqueous Phase Contaminants. Dissertation. Colorado State University, 2010. Sivaswamy, V., Boyanov, M. I., Peyton, B. M., Viamajala, S., Gerlach, R., Apel, W. A., Sani, R. K., Dohnalkova, A., Kemner, K. M., Borch, T. , Multiple mechanisms of uranium immobilization by Cellulomonas sp. strain ES6. Biotechnology and Bioengineering, 2011. doi: 10.1002/bit.22956 Blotevogel, J., Borch, T., Desyaterik, Y., Mayeno, A.N., Sale, T.C. Quantum Chemical Prediction of Redox Reactivity and Degradation Pathways for Aqueous Phase Contaminants: An Example with HMPA. Environ. Sci. Technol. 2010, 44, 5868-5874. Yang, Y.-Y., Borch, T., Young, R. B., Goodridge, L. D., Davis, J. G., Degradation Kinetics of Testosterone by Manure-Borne Bacteria: Influence of Temperature, pH, Glucose Amendments, and Dissolved Oxygen. Journal of Environmental Quality 2010, 39, 1153-1160. Borch, T., Kretzschmar, R., Kappler, A., Van Cappellen, P., Ginder-Vogel, M., Voegelin, A., Campbell, K. M., Biogeochemical Redox Processes and their Impact on Contaminant Dynamics. Environ. Sci. Technol. 2010, 44, 15-23. Amstaetter, K., Borch, T., Larese-Casanova, P., Kappler, A. Redox transformation of arsenic by Fe(II)-activated goethite (±-FeOOH). Environmental Science & Technology, 2010, 44, 102-108 Kocar, B.D., Borch, T., Fendorf, S. Arsenic Mobilization and Repartitioning during Biogenic Sulfidization and Transformation of Ferrihydrite. Geochimica et Cosmochimica Acta, 2010, 74, 980-994. Stephen A. Boyd, Cliff T. Johnston, David A. Laird, Brian J. Teppen, and Hui Li, 2010, Comprehensive Study of Organic Contaminant Adsorption by Clays: Methodologies, Mechanisms and Environmental Implications. In volume3: Biophysico-Chemical Processes of Anthropogenic Organic Compounds in Environmental Systems. Edited by Baoshan Xing, Nicola Senesi, and P. Ming Huang. Wan-Ru Chen, Yunjie Ding, Cliff T. Johnston, Brian J. Teppen, Stephen A. Boyd, and Hui Li, 2010, Reaction of Lincosamide Antibiotics with Manganese Oxide in Aqueous Solution. Environmental Science and Technology, 44:4486-4492. Yunjie Ding, Weihao Zhang, Cheng Gu, Irene Xagoraraki, and Hui Li, 2010, Determination of Pharmaceuticals in Biosolids using Pressurized Liquid Extraction and Liquid Chromatography/Tandem Mass Spectrometer. Journal of Chromatography A. doi:10.1016/j.chroma.2010.10.112. Cheng Gu, Hanzhang Jia, Hui Li, Brian J. Teppen, and Stephen A. Boyd, 2010, Highly Reactive Subnano-Sized Zero-Valent Iron Synthesized on Smectite Clay Templates. Environmental Science and Technology, 44:4258-4263. Hanzhong Jia, Cheng Gu, Stephen A. Boyd, Brian J. Teppen, Cliff T. Johnston, Cunyi Song, and Hui Li, 2011, Comparison of Reactivity of Nanosized Zero-Valent Iron on Clay Surfaces. Soil Science Society of America Journal doi:10.2136/sssaj2010.0080nps. Cun Liu, Hui Li, Brian. J. Teppen, Cliff. T. Johnston, and Stephen. A. Boyd, 2009, Mechanisms Associated with the High Adsorption of Dibenzo-p-dioxin from Water by Smectite Clays. Environmental Science and Technology, 43:2777-2783. Joseph J. Pignatello, Brian Katz, and Hui Li, 2010, Organic Contaminants in Water, Soil and Sediment: Sources, Interactions and Ecological Impacts: An Introduction to the Special Series. Journal of Environmental Quality, 39:1133-1138. Wenlu Song, Yunjie. Ding, Cary T. Chiou, and Hui Li, 2010, Selected Veterinary Antibiotics in Agricultural Water and Soil Resulting from Animal Feeding Operations. Journal of Environmental Quality, 39:1211-1217. Cuiping Wang, Yunjie Ding, Brian J. Teppen, Stephen A. Boyd, and Hui Li, 2009, Role of Interlayer Hydration in Lincomycin Sorption by Smectite Clays. Environmental Science and Technology, 43:6171-6176. Weihao Zhang, Yunjie Ding, Stephen A. Boyd, Brian J. Teppen, and Hui Li, 2010, Sorption and Desorption of Carbamazepine from Water by Smectite Clays. Chemosphere 81:954-960. Stone, J.J., S.A. Clay, and G.M. Spellman. 2010. Tylosin and chlortetracycline effects during swine manure digestion: Influence of sodium azide. Bioresource Technol. 101: 9515-9520. Rettedal, E.A., S.Clay, and V.S. Brözel. 2010. GC-Clamp primer batches yield 16S rRNA amplicon pools with variable GC clamps, affecting denaturing gradient gel electrophoresis profiles. FEMS Microbiology Letters 312:55-62. Lehnert Nelson, K., V.S. Brözel, S.A. Gibson, R. Thaler, and S.A. Clay. 2010. Influence of manure from pigs fed chlortetracycline as grown promotant on soil microbial community structure. World J. Microbiol Biotechnol. Online 7/14/10 Alavi, G., M. Chung, J. Lichwa, M. DAlessio, and C. Ray. 2011. The fate and transport of RDX, HMX, TNT, and DNT in the volcanic soils of Hawaii: A laboratory and modeling study, Journal of Hazardous Materials, 185: 1600-1604. Mohanram, A., C. Ray, R. W. Harvey, D. Metge, J. N. Ryan, J. Chorover, and D.D. Eberl. 2010. Comparison of transport and attachment behaviors of Cryptosporidium parvum oocysts and oocyst-sized microspheres being advected through three minerologically different granular porous media, Water Research, 44: 5334-5344, doi:10.1016/j.watres.2010.06.015. Dusek, J., Alavi, G., T. Vogel, and C. Ray. 2010. Effect of plastic mulch on water flow and herbicide transport in soil cultivated with pineapple crop: A modeling study, Agric. Water Management, 97: 1637-1645. Dusek, J., M. Sanda, B. Loo, and C. Ray. 2010. Field leaching of pesticides at five test sites in Hawaii: study description and results, Pest Management Science, 66(6): 596-611.

Impact Statements

Soil pH can be used as an indicator for the potential mobility of lincomycin to groundwater. Management practices for the application of treated sewage effluent containing lincomycin can be optimized based on soil pH to prevent groundwater contamination.
In the soils tested there seems to be no increase in the development of antibiotic resistance (AR) under treated effluent recharge. Comparing the development of AR in soil bacteria at these two sites has increased current knowledge of reclaimed water safety, and will allow water professionals nationwide to make more informed decisions concerning the use of reclaimed water, while protecting both public and environmental health.
Results suggest that pesticide residues remain on concrete and are available for contaminating runoff for a prolonged time. Working with California Department of Pesticide Regulation, we are providing baseline information as well as scientifically based options that may be used by a range of stakeholders, such as professional pesticide applicators and manufacturers, to mitigate pesticide runoff and potential contamination to urban streams.
Newly isolated organisms will allow scientists to obtain a better understanding of the biochemistry and genetics of acetanilide herbicides catabolism by microorganism, and will provide new tools for the bioremediation of environments impacted by these herbicides.
Results of these studies indicate that microorganisms comprising two main branches of the tree of life have acquired the ability to degrade the same novel chlorinated herbicide that has been recently added to the biosphere. The isolated Bacillus and Candida microorganisms provide insight into the evolution of biodegradation ability of anthropogenic compounds and may provide as means to bioremediation of water and soil environments contaminated by these herbicides.
Results of these studies show that the bioavailabilities of atrazine were similar when formulated with organoclays or as free atrazine. These results indicated that while atrazine can formulated as organoclay complexes, it is still accessible to degrading bacteria, and the removal of this herbicded can be achieved by soil microorganisms. Our results also are useful to mitigate the impact of use of atrazine in the environment.
Results of these studies provide a mecahnistic inderstanding of how bacterial enzymes degrade atrazine and other triazine herbicides. Results from these studies can be used to develop enyzmes with greater affinity for atrazine and with faster reaction rates so that atrazine remediation in the environment can be achoved in a cost and time efficient manner.
Hawaii used data from studies to evaluate leaching, potential loss to runoff water, and ecotoxicological impacts, and provides that data to the state regulatory agency for action. If the compound appears to have significant impact to the local environment, it may be registered as a restricted use compound or the state requires that a certified applicator be responsible for its use. In that way, the state keeps track of the amount used and the locations treated.

Date of Annual Report: 03/01/2012

Report Information

Annual Meeting Dates: 01/04/2012 - 01/05/2012
Period the Report Covers: 10/01/2010 - 09/01/2011

Participants

Clinton Williams (USDA-ARS, Arizona); Jack Watson (Pennsylvania State University); Bill Koskinen (USDA-ARS, St. Paul, MN); Ron Turco (Purdue University); Sharon Clay (South Dakota State University); Dino DeCiantis(Penn State University); Shad Nelson (Texas A&M, Kingsville); Keith Goyne (University of Missouri); Lee Sommers(Colorado State University)

Brief Summary of Minutes

Shad Nelson served as Chair of the committee and Joe Pignatello served as Secretary. The Administrative Advisor, Lee Sommers, summarized the vision and roles of NIFA and discussed the AFRI grants program. Each participant provided a research update, with discussion following each presentation. Thank you to all who were able to participate! Thomas Borch, from Colorado State University will serve as our Secretary the next two years, while Joe Pignatello will serve as the Chair. Based on discussion of the participants and emails sent prior to the meeting, we decided to schedule the meeting next year on January 23 and 24 in Fort Collins, CO. Thank you to our Administrative Advisor, Dr. Lee Sommers, for being willing to host us! There is always a weather risk in traveling to Ft. Collins during that time of year, but on the other hand, if we get snowed in we can probably find some winter sports nearby to keep us entertained! (and it will be more pleasant than St. Paul! :)!). It is likely we will have accommodations within easy walking distance from campus and a shuttle from the Denver airport is about $30 or so. This timing hopefully helps those of us who find it difficult to get away during the first weeks of spring semester / winter quarter due to classes.

Accomplishments

Objective 1: To identify and quantify fundamental chemical, physical, and biological processes relevant to pesticides and contaminants in agricultural ecosystems I. University of Hawaii, at Manoa (J-P Bingham) A. Development and environment testing of novel peptide molluscicdes Accomplishment/output: The objective is to identify new biodegradable pesticide agents against invasive snails and determine their application and residual contribution in agricultural ecosystems. Cone Shells (genus Conus) represent an untapped library of peptides that specifically target conserved physiological mechanisms within snails. These mechanisms represent novel targets for agricultural molluscicide development. These species represent a novel source of molluscicides. Isolation of three bioactive peptides have been undertaken, the synthesis of these native-like peptides has then demonstrated a level of peptide degradation in solid. These are now being compared to a newly bioengineered versions of these toxin, namely the C- to N- cyclized versions that possess a higher orally activity in mice and demonstrate a higher rate of absorption in snails upon topical application. B. Evaluating the Risk of Diphacinone Rodenticide Pellets to Hawaiian Trigger Fish Accomplishment/output: Polynesian rats introduced on the island of Lehua in 1931 are highly detrimental to native vegetation and the eggs of seabirds. To exterminate the invasive rats, the anticoagulant rodenticide Diphacinone applied in pellets was used between December 2008 and February 2009, leaving a buffer zone around the shorelines, but nevertheless causing a fish die-off. Fish are exposed to Diphacinone by direct ingestion, indirect ingestion, and through absorption of dissolved rodenticide in the water. Our objective was to determine the effects for Diphacinone on Trigger fish using a closed model system, focusing on behavior, food consumption rates, palatability of pellets containing Diphacinone, and Diphacinone toxicity and accumulation in Trigger Fish. We are present developing both HPLC and LC/MS methods to quantify Diphacinone. II. Colorado State University, Fort Collins (Thomas Borch) A. Prediction and Analysis of Contaminant Persistence. Accomplishment/output: We investigated a quantum chemical approach to evaluate the fate of contaminants of emerging concern, applied here to hexamethylphosphoramide (HMPA), a widely used solvent and potential groundwater contaminant. Oxidation of HMPA is estimated to require at least iron-reducing conditions at low-to-neutral pH and nitrate-reducing conditions at high pH. Furthermore, the transformation of HMPA by permanganate is predicted to proceed through sequential N-demethylation. Experimental validation based on LC/TOF-MS analysis confirms the predicted pathways of HMPA oxidation by permanganate. The calculations also predict PN bond hydrolysis to be the only thermodynamically favorable reaction that may lead to its degradation under reducing conditions. It is predicted that HMPA hydrolyzes via an acid-catalyzed mechanism at pH < 8.2, and an uncatalyzed mechanism at pH 8.2-8.5. The estimated half-lives of thousands to hundreds of thousands of years over the groundwater-typical pH range of 6.0 to 8.5 indicate that HMPA will be persistent in the absence of suitable oxidants. We also we developed a new RPLC/ESI-TOF-MS method and further investigated the chromatographic performances of two columns. B. Artificial Sweeteners as Indicators for Anthropogenically Influenced Water. Accomplishment/output: Artificial sweeteners can be used as indicator compounds for wastewater influence on other water types. The objective of this work was to quantify sucralose in select U.S. drinking water systems. Water samples from 19 United States (U.S.) drinking water treatment plants (DWTPs) serving more than 28 million people were analyzed for sucralose using liquid chromatography tandem mass spectrometry (LC-MS/MS). Sucralose was found to be present in source water of 15 out of 19 DWTPs (472900 ng/L), finished water of 13 out of 17 DWTPs (492400 ng/L) and distribution system water of 8 out of the 12 DWTPs (482400 ng/L) tested. Sucralose displayed low removal (12% average) in the DWTPs. It was found persist regardless of the presence of residual chlorine or chloramines. In order to understand intra-DWTP consistency, sucralose was monitored at one drinking water treatment plant over an 11 month period from March 2010 through January 2011, and averaged 440 ng/L in the source water and 350 ng/L in the finished water. III. South Dakota State University, Brookings, SD A. Sorption and bioavailability of potentially toxic compounds produced from selected pesticides and pharmaceuticals in soil-water matrices and biological systems. Accomplishments/output: The studies focused on the effect of chlortetracycline on anaerobic manure decomposition, the impacts of tylosin- and chlortetracycline-containing manure on soil nutrients and soil microbial community structure, and sorption of herbicides to soils amended with biochars produced by microwave pyrolysis. High doses of chlortetracycline inhibited sequence batch reactors efficiencies, although total gas production was greater. Aged manure containing tylosin inhibited CO2 production the most in batch reactors. Sorption of atrazine, dicamba and 2,4-D to biochar alone was always greater than to soil alone. However, addition of 1 or 10% biochar to soil increased sorption only modestly, if at all. IV. University of Hawaii, Honolulu, HI (C. Ray) A. Transport of Cryptosporidum parvum oocysts in variable charge soils. Accomplishments/output: We studied the effect of dissolved organic carbon on the transport and attachment behavior of Cryptosporidium parvum oocysts and 1.8 micrometer polystyrene microspheres in a red, Fe-, Al-, and clay-rich volcanic soil from Oahu (called Poamoho soil), and an organic- and quartz-rich soil from Illinois (Drummer soil). Experiments were conducted using flow-through columns with or without 100 mg/L sodium dodecyl benzene sulfonate (SDBS) or Suwanee River Humic Acid (SRHA) in the influent. SDBS increased transport but SRHA reduced of microspheres through the soils. SDBS increased oocysts transport through Drummer, but no enhanced oocyst transport was detected in the Poamoho soil. SRHA slightly increased oocysts transport in Poahomo soil, but caused a 6-fold increase in transport through the Drummer soil. V. North Dakota State University, Fargo ND (Tom M. DeSutter) A. Manure management effects on 17²-estradiol Accomplishments/output: We investigated the association of the estrogen hormone 17²-estradiol with the soil solid phase when liquid manure was introduced. 17²-estradiol persisted in the solution phase longer when liquid swine manure was present compared to calcium chloride. The log Koc values were greater in the absence than the presence of swine manure. VI. University of California, Riverside (Jay Gan) A. Bioavailability and phase partition of hydrophobic contaminants: Accomplishments/output: Sorption isotherms were constructed for, polybrominated diphenyl ether (PBDE) flame retardants, BDE-47 and BDE-99, in sediments by different methods to measure the aqueous phase concentration Cw. The Cw measured by automated solid phase microextraction (Cw-SPME) was consistently smaller than by liquid-liquid extraction (Cw-LLE), suggesting substantial association of PBDEs with DOC. We evaluated biodegradation of pyrene by Mycobacterium vanbaalenii PYR-1 as a function of sediment particle sizes, and investigated the relationship between the rate of degradation on sand, silt and clay particles with their individual desorption kinetics measured with the Tenax extraction method. The fractions mineralized after 336-h incubation greatly surpassed the rapidly desorbing fraction (Frapid) values, suggesting utilization of pyrene in the slow desorption pool (Fslow). Model analysis showed that pyrene sorbed on silt and clay aggregates was directly utilized by the degrading bacteria. Like black carbon (BC) particles, single-wall carbon nanotubes (SWCNT) have a high affinity for hydrophobic organic contaminants (HOCs) and therefore the presence of SWCNT in sediment may lead to altered bioavailability of HOCs. We compared SWCNT with biochar and charcoal for their effect on the microbial degradability of 0.05 mg kg-1 14C-phenanthrene (PHE) by Mycobacterium vanbaalenii PYR-1 in two sediments. When the amendment rate of adsorbent was 1 mg g-1, PHE mineralization was inhibited much more significantly by SWCNT than by either biochar or charcoal, apparently due to its much larger specific surface area and pore volume. However, pre-interaction of SWCNT with dissolved organic matter led to attachment of polar molecules and reduced surface area on SWCNT, resulting in decreased PHE sorption and an alleviated effect on PHE biodegradation, in the order of peptone > tannic acid > humic acid. B. Characterizing pesticide sorption and washoff on concrete: Accomplishments/output: Use of pesticides around residential homes is linked to contamination of urban waterways, where impervious surfaces like concrete are considered as sources or facilitators of the contamination. Sorption of 14C-permethrin to concrete was rapid, but both the parent compound and total 14C showed an initial rapid desorption followed by prolonged slow desorption. Permethrin became more resistant to desorption as the pesticide contact time on the concrete increased. The decreased desorption was partially attributed to decomposition. Runoff from concrete 1 d after pesticide treatment contained high levels of bifenthrin and permethrin. Although runoff levels decreased over time, detectable residues were still found in runoff water after 3 months. ANOVA analysis showed that precipitation intensities and concrete surface conditions (i.e., acid wash, silicone seal, stamping, and addition of microsilica) did not significantly affect the pesticide transferability to runoff. C. Characterizing sorption and transformations of emerging contaminants. Accomplishments/output: Soil sorption and degradation are important processes affecting the leaching potential of trace contaminants in irrigated soil. We examined the sorption and attenuation of six psychoactive and antilipidemic drugs, carbamazepine, diazepam, dilantin, meprobamate, primidone, and gemfibrozil, in a loam (LVL) and a loamy sand (ALS) representaitve of golf course soils in the southwestern United States. For the same soil, the sorption affinity generally followed a decreasing order diazepam > carbamazepine > gemfibrozil > dilantin H meprobamate H primidone. While dilantin, gemfibrozil and meprobamate showed moderate persistence under aerobic conditions, , the test compounds were recalcitrant to degradation in the other treatments. We evaluated sorption and degradation in two soils collected from arid regions of five antibiotic and anti-inflammatory drugs, naproxen, trimethoprim, diclofenac, ibuprofen and sulfamethoxazole. Degradation was influenced by microbial activities, oxygen status in the soil, soil type and compound characteristics. Bisphenol F (BPF) is widely used in polycarbonate plastics and epoxy resins. This study considered oxidation of BPF by MnO2, a commonly occurring metal oxide in soil. MnO2 efficiently oxidized BPF. The reaction was pH dependent and influenced by cosolutes including humic acids, metal ions and anions. Five reaction intermediates were identified. VII. USDA-ARS, St. Paul, MN (William Koskinen) A. Sorption and sorption reversibility of herbicides Indaziflam, Aminocyclopyrachlor Accomplishments/output: Sorption and desorption of indaziflam and aminocyclopyrachlor in soils from Brazil and the USA, with different physical chemical properties, were investigated. The Freundlich parameters suggest low to moderate mobility for indaziflam and high mobility for aminocyclopyrachlor. However, sorption was hysteretic for both compounds on all soils. B. Metolachlor and Mesotrione degradation Accomplishments/output: Metolachlor (2-chloro-6-ethyl-N-(2-methoxy-1-methylethyl) aceto-o-toluidide) is a pre-emergent chloroacetanilide herbicide used to control broadleaf and annual grassy weeds in a variety of crops. In this study we examined respectively, for microorganisms that had the ability to degrade this herbicide. We report here on the isolation and characterization of pure cultures of Candida xestobii and Bacillus simplex, from a silty-clay soil (a Luvisol) from Spain with 10 and 2 year histories of metolachlor and S-metolachlor applications, that have the ability to use metolachlor as a sole source of carbon for growth. Moreover, the yeast degraded other acetanilide compounds; acetochlor and alachlor. Mesotrione is a benzoylcyclohexane-1,3-dione herbicide that inhibits 4-hydroxyphenyl pyruvate dioxygenase (HPPD) in target plants. Mesotrione-degrading bacteria were selected among strains isolated from Brazilian aquatic environments, located near corn fields treated with this herbicide. Pantoea ananatis was found to rapidly and completely degrade mesotrione, although mesotrione did not serve as a sole C, N, or S source for growth of P. ananatis, and mesotrione catabolism required glucose supplementation to minimal media. Intermediates were identified other than 2-amino-4-methylsulfonyl benzoic acid (AMBA) or 4-methylsulfonyl-2-nitrobenzoic acid (MNBA), two metabolites previously identified in a mesotrione-degrading Bacillus strain. VIII. University of California, Davis Davis, CA (Sanjai J. Parikh) A. Examining the potential for rapid transport of veterinary antibiotics to groundwater. Accomplishments/output: Groundwater samples were obtained from two monitoring wells concurrent with fertigation of an agricultural field at a dairy facility in the Central Valley of California. Eight common veterinary antibiotics (oxytetracycline, chlortetracycline, sulfamethazine, sulfamerazine, sulfadiazine, sulfamethoxazole, sulfadimethoxine, and monensin) used in the dairy industry were targeted for analysis. Analytical method development was carried out and established limits of quantification (LOQ). Sulfadimethoxine and monensin were detected in the lagoon water ranging from 16.4 ng L-1 to 116 ng L-1 and 159 ng L-1 to 4772 ng L-1, respectively. In groundwater, sulfadimethoxine, sulfamethazine, and monensin were commonly measured with reliable reporting levels above the LOQ between 1.33 ng L-1 to 20.6 ng L-1. Analysis of general water chemistry indicate that the lagoon water and hence, antibiotics did not reach the groundwater. Instead, the results suggest that antibiotics were present before the irrigation season and indicate persistence in the groundwater. B. Role of soil minerals on sorption and facilitated transport of veterinary antibiotics. Accomplishments/output: Preliminary sorption data reveals no sorption of sulfamethazine to the mineral phases studied except birnessite and therefore suggest facile transport through soil. For monensin, only goethite was shown to bind monensin. Goethite is positively charged and monensin is negatively charged within the pH range. The decreased sorption of monensin to goethite with increasing ionic strength suggests an outer-sphere mechanism. In the current study, increased functionalization of sulfamethazine observed upon reaction with ´-MnO2 indicates cleaving of aromatic rings, and that abiotic degradation is occurring. C. Impact of biochar soil amendments on pesticide and pharmaceutical transport in soil. Accomplishments/output: Addition of a highly sorbing material at the time of biosolid application would serve to reduce the bioavailability of the wide range of hydrophobic compounds found in biosolids, and support beneficial reuse of organic wastes, such as biosolids and agricultural materials (e.g., walnut shells). We examined sorption of the fluoroquinolone antibiotic ciprofloxacin used in human medicine and of the phenylurea pesticides, linuron, diuron, and monuron, Yolo silt loam, kaolinite, biochar (wood feedstock and walnut shell), activated carbon, biosolids and a soil/biochar and biosolid mixture. Our results demonstrate that ciprofloxacin has high sorption affinity to walnut shell biochar and activated carbon, moderate sorption to kaolinite and low sorption to woodstock biochar. The results suggest that walnut shell biochar used as a co-amendment with biosolids could limit the bioavailability of the antibiotic ciprofloxacin when applied to soil. IX. University of Nebraska-Lincoln (Patrick J. Shea) A. Production of N-nitrosoatrazine and Adsorption-desorption of atrazine and N-nitrosoatrazine in soil. Accomplishments/output: In the companion project (NEB-38-069), NNAT formed readily from atrazine (pKa = 1.7) and nitrite in solution at pH 2-4 and in soil at pH d5. Simazine (pKa = 1.62) also formed nitrososimazine. NNAT degrades to atrazine and hydroxyatrazine. NNAT formation is catalyzed by acetate acid and fulvic acid in water at pH 5 to 7, but not by humic acid. NNAT half-life in Aksarben soil was about 9 d, with degradation to atrazine and other compounds. We studied the soil adsorption-desorption behavior of atrazine and N-nitrosoatrazine (NNAT), formed from reaction of atrazine with nitrite under acidic conditions. The pH was adjusted to 3-8. Adsorption and desorption Kd and Koc values indicated greater adsorption of NNAT than atrazine, and greater hysteresis of NNAT than atrazine. Soil texture was important. The Kd for NNAT and atrazine increased when bentonite clay was treated with dodecyltrimethylammonium bromide (DDTMA) or tannic acid (TAC) DDTMA or TAC, indicating that adsorption was further increased by coating the clay with organic material. X. Connecticut Agricultural Experiment Station, New Haven (J. Pignatello) A. Adsorption of Ionizable Compounds to Black Carbon Accomplishments/output: Black carbon is a natural constituent of soils and amendment of soil with manufactured black carbon (biochar) has attracted interest as a way to improve soil fertility and store carbon. While adsorption of nonionic compounds to black carbon has been extensively studied, far less attention has been paid to ionic and ionizable compounds. The intensity of adsorption of ionic compounds, even negatively charged compounds, is surprisingly strong. We have identified some unique reactions of ionizable compounds on charcoals. Adsorption of organoanions, such as aromatic acid anions (cinnamic acid, coumaric acid) and the sulfonamide anion of the veterinary antimicrobial, sulfamethazine, release hydroxide ion upon adsorption. The resulting neutral molecule engages in an especially strong hydrogen bond with a carboxyl or phenoxyl group on the surface known as a negative charge-assisted H-bond. Sulfamethazine acquires a positive charge as pH decreases due to protonation of the amino group on the p-aminosulfonamide ring. In addition to charge pairing with surface negatively charged sites, this charged ring system was shown to engage in a pi-pi electron donor-acceptor interaction with the polyaromatic surface of graphitic microcrystallites of which black carbon is composed. This interaction is a result of the electron-deficient p-aminosulfonamide ring due to the withdrawing properties of the sulfonamide and positively charged amino groups ring, interacting with the electron-rich and polarizable polyaromatic surface. B. Predicting Sulfamethazine Adsorption in Biochar-Amended Soil. Accomplishments/output: Biochar has been shown to be a beneficial soil amendment in some agricultural applications. Since charcoal can be a potent sorbent, we sought to determine whether four commercial prototype biochars could predictably reduce pore water concentrations of the veterinary antimicrobial, sulfamethazine (SMT) in St. Joan loam soil (Spain). The adsorbed-to-dissolved concentration ratio log Kd,BC of SMT increased exponentially with properties that reflect degree of carbonization and micropore development in the biochar. Except for the biochar produced by fast pyrolysis, Kd,BC was between 10^1 and 10^5 times greater than the soil organic carbon-normalized distribution ratio (KOC) of SMT, depending on the biochar and SMT concentration. The pH dependence of Kd,BC between 5 and 8 was consistent with strong H-bonding of the anion of SMT with a surface oxyl group that we proposed earlier. While as expected addition of biochar to soil (1% or 2%) increased the Kd of the mixture in relation to soil alone in proportion to the Kd,BC of the biochar, the increase was overestimated by the sum of sorption to the two components by as much as 10^2 due to weathering effects. Weathering is most likely due to fouling of the biochar by humic substances. Most of the weathering took place already after the shorter of the two weathering regimes tested (20 oC, 48 h biochar-soil pre-wetting, followed by 48 h sorption). C. Preparation and Characterization of Humic Acid Cross-linked with Organic Bridging Groups. Accomplishments/output: Cross-linking of humic substances with organic bridging groups is thought to contribute to soil organic matter humification and according to polymer theory is expected to alter its sorbent properties. Model cross-linked humic substances were prepared by cross-linking Amherst soil humic acid by a diepoxide and a polycarboxylic acid in the solid state, applying procedures established for cross-linking of polymers and textile fabrics. Physicochemical properties of the products were determined by solubility experiments and thermal analysis. The incorporation of the cross-linker into the matrix of the humic acid by covalent linkages was confirmed by both the disappearance of bands of the reactive functional groups of the cross-linker in the FTIR spectrum and the increase of signals related to the incorporation of the cross-linker into the matrix of the humic acid in the FTIR and 13C-CPMAS-NMR spectra. The formation of covalent ester and ether linkages by the cross-linking reaction was indicated. Water solubilities at pH 6.2 of the cross-linked samples as determined by UV/Vis spectrometry were reduced compared to controls. Fewer water molecule bridges were formed in the cross-linked samples, which was attributed to a lower number of available functional groups and increased distances between humic acid strands caused by the cross-linking molecules. Reduced reactivities of humic acid strands in the cross-linked samples further indicated successful cross-linking. Objective 2: Integrate chemical and biological process information for use in models applicable across different spatial and temporal scales. I. University of Hawaii, Honolulu (C. Ray) A. Transport of selected endocrine disrupting chemicals from wastewater through a Hawaiian Oxisol. Accomplishments/output: We continued experiments on the leachability of two estrogen hormones (17-beta estradiol [E2] and estrone [E1]) introduced simultaneously through an intact soil core (15 to 45 cm) of an Oxisol from Oahu. The soil columns were eluted with municipal wastewater that has gone through treatment, filtration, and UV disinfection (TOC content 7.7 mg/L). Both compounds started to breakthrough around 12 pore volumes; however, the rate of breakthrough of E1 was much faster than that of E2. After 66 pore volumes, the column was flushed with deionized water 1 mM CaCl2. Bromide was fully flushed out of the column within 5 more pore volumes. The flushing continued for 18 more pore volumes and during that time 75% of E1 and 40 of E2 were removed. B. Sewage biomarkers to assess infiltration of rainwater into municipal sewer systems. Accomplishments/output: The infiltration of heavy rainfall to sewer systems increases treatment costs and the chance of overflow of untreated sewage to receiving waters. Selected chemical and biological markers of sewage (caffeine, total N, suspended solids, E. coli, and enterococci) were monitored during wet and dry weather conditions. Rainfall derived infiltration was determined independently by measuring flow in sewers or by marker concentrations. II. University of Nebraska-Lincoln (Patrick J. Shea) A. Adaption of a watershed vulnerability model to atrazine. Accomplishments/output: The components of a watershed-scale vulnerability model (developed in a USDA-NIWQP project) were analyzed, converted to a GIS, and adapted to the field scale using SSURGO and field data, with a goal of finding the best resolution for raster maps. Model output was generated for the acid-sensitive herbicide, atrazine, on the day of application and 7 days after application for a 35-ha field in north-central Missouri, an intensely row-cropped agricultural field with claypan soils located in Major Land Resource Area 113. The initial model showed how acid-catalyzed hydrolysis of atrazine would reduce vulnerability to solution runoff in the north part of a Missouri test field. Vulnerability to leaching in the test field was comparatively lower than to solution runoff. An early version of the watershed model had overpredicted leaching vulnerability due to the presence of claypans in the Missouri study area. Because a claypan is not a diagnostic horizon, identification criteria for a surface restrictive layer were developed based upon the Nebraska Rainwater Basins and Missouri claypans. A runoff penalty (which increases vulnerability) was created based on the large pore volume (saturated 0.33 bar moisture) above the clay restrictive layer or depth to free water, whichever is shallower. Using these criteria, a clay restrictive layer was identified in the southern Blue River Basin, an area with atrazine runoff problems. Objective 3. Provide stakeholders with tools for developing strategies to ensure sustainable agriculture and to protect natural resource systems. I. University of Hawaii, Honolulu (C. Ray) A. Registration of New Chemicals in Hawaii Accomplishments/output: Hawaii is one of the few states in the union that does not automatically accept the registration of a given chemical issued by USEPA. If the compound is going to be used over a large area and has the potential to leach to ground water, the state conducts in-house evaluation of its environmental impact. If the impact exceeds a pre-judged score, the University of Hawaii is asked to complete a detailed assessment of its potential to leach to ground water. For this purpose, the registrant provides copies of all fate and transport studies used in EPAs registration process. We used data from these studies to evaluate leaching, potential loss to runoff water, and ecotoxicological impacts. In the current year, we are re-evaluating our pesticide registration decisions based on new data provided by selected registrants. II. University of Nebraska-Lincoln (Patrick J. Shea) A. Identification of variables affecting atrazine runoff from subwatersheds. Accomplishments/output: The impacts of corn and sorghum planting progress (indicating atrazine application), rainfall, antecedent soil water content, and the presence of a soil surface restrictive layer on stream-measured weekly atrazine load for 1997-2004, were determined for independent subwatersheds of the NE-KS Blue River Basin. Analysis of atrazine monitoring data showed maximum atrazine runoff after most of the corn had been planted but during sorghum planting from mid-May to early June, immediately following multiple rainfall events that saturated the soil profile and caused runoff from fields. Analysis of covariance showed rainfall was the most significant factor associated with atrazine loading, but soil water content, corn and sorghum planting progress, and the presence of a soil surface restrictive layer were also important.

Publications

Gan, J., S. Bondarenko, L. Oki, D. Haver, and J.X. Li. 2011. Occurrence of fipronil and its biologically active derivatives in urban residential runoff. Environmental Science & Technology (in press). Jiang, W.Y., D. Haver, M. Rust, and J. Gan. Runoff of pyrethroid insecticides from concrete surfaces following simulated and natural rainfalls. 2012. Water Research (in press). Lin, K.D., S. Bondarenko, and J. Gan. 2011. Sorption and persistence of wastewater-borne psychoactive and antilipidemic drugs in soils. Journal of Soils and Sediments 11:13631372. Haruta, S., W.T. Jiao, W.P. Chen, A.C. Chang, and J. Gan. 2011. Evaluating Henrys law constant of N-nitrosodimethylamine (NDMA). Water Science and Technology 64: 1636-1641. Delgado-Moreno, L., K.D. Lin, R. Veiga-Nascimento, and J. Gan. 2011. Occurrence and toxicity of three classes of insecticides in water and sediment in two Southern California Coastal watersheds. Journal of Agricultural and Food Chemistry 59: 9448-9456. Lao, W.J., and J. Gan. 2011. Enantioselective degradation of warfarin in soils. Chirality (in press) Lu, Z.J., K.D. Lin, and J. Gan. 2011. Oxidation of bisphenol F (BPF) by manganese dioxide. Environmental Pollution 159: 2546-2551. Cui, X.Y., F. Jia, Y.X. Chen, and J. Gan. 2011. Influence of single-walled carbon nanotube on microbial availability of phenanthrene in sediment. Ecotoxicology 20:1277-1285. Budd, R., A. OGeen, K. Goh, S. Bondarenko, and J. Gan. 2011. Removal mechanisms and fate of insecticides in constructed wetlands. Chemosphere 83: 1581-1587. Lin, K.D., and J. Gan. 2011. Sorption and degradation of wastewater-associated non-steroidal anti-inflammatory drugs and antibiotics in soils. Chemosphere 83: 240-246. Cui, X.Y., W. Hunter, Y. Yang, Y.X. Chen, and J. Gan. 2011. Biodegradation of pyrene in sand, silt and clay fractions of sediment. Biodegradation 22:297307 Liu, W.P., H.H. Zhang, B.P. Cao, K.D. Lin, and J. Gan. 2011. Oxidative removal of bisphenol A using zero valent aluminum-acid system. Water Research 45: 1872-1878. Wang, W., L. Moreno, Q.F. Ye, and J. Gan. 2011. Improved measurements of partition coefficients for polybrominated diphenyl ethers (PBDEs). Environmental Science & Technology 45: 1521-1527. Jiang, W., J. Gan, and D. Haver. 2011. Sorption and desorption of pyrethroid insecticide permethrin on concrete. Environmental Science & Technology 45: 602-607. Derby, N., H. Hakk, F. Casey, and T. DeSutter. 2011. Effects of composting swine manure on nutrients and estrogens. Soil Sci. 176:91-98. Schuh, M.C., F.X.M. Casey, H. Hakk, T.M. DeSutter, K.G. Richards, E. Khan, and P. Odour. 2011. An on-farm survey of spatial and temporal stratifications of 17²-estradiol concentrations. Chemosphere 82:1683-1689. Schuh, M.C., F. Casey, H. Hakk, T.M. DeSutter, K.G. Richards, and E. Khan. 2011. Effects of field-manure applications on stratified 17²-estradiol concentrations. J. Haz. Mat. 192:748-752. Zitnick, K.K., N.W. Shappell, H. Hakk, T.M. DeSutter, E. Khan, and F.X. Casey. 2011. Effects of liquid swine manure on dissipation of 17²-estradiol in soil. J. Haz. Mat. 186:1111-1117. Bai, X., F.Casey, H. Hakk, S. Shrestha, T. DeSutter, E. Khan, and P. Odour. 2011. Modeling sorption and degradation of 17²-estradiol-17-sulfate in agricultural soils. In Annual meeting abstracts [CD-ROM]. ASA, CSSA, and SSSA, Madison, WI. Bai, X., F.X.M. Casey, H. Hakk, S.L. Shrestha, T. DeSutter, E. Khan, and P.G. Odour. 2011. Modeling sorption and degradation of 17B-estradiol-17-sulfate in agricultural soils. Abstracts AGU Fall Meeting, San Francisco, CA. Bai, X., F.X.M. Casey, T.M. DeSutter, H. Hakk, P.G. Odour, and E. Khan. 2011. Sorption and degradation of 17beta-estradiol-17sulfate in agricultural soils. 54th Annual Manitoba Soil Science Society Conference. Winnipeg, MB, Canada. Chambers, K., F. Casey, H. Hakk, N.W. Shappell, T. DeSutter, and E. Khan. 2011. Bioavailability of colloidal organic carbon bound estrogen. In Annual meeting abstracts [CD-ROM]. ASA, CSSA, and SSSA, Madison, WI. Mohanram, A., C. Ray, D.W. Methge, L.B. Barber, J.N. Ryan, and R.W. Harvey. 2011. Effect of Dissolved Organic Carbon on the Transport and Attachment Behaviors of Cryptosporidium parvum oocysts and Carboxylate-Modified Microspheres Advected through Temperate Humic and Tropical Volcanic Agricultural soil, Environmental Sci. Tech, (DOI: 10.1021/es2003342) Shelton, J., L. Kim, J. Fang, C. Ray, and T. Yan. 2011. Assessing the Severity of Rainfall Derived Infiltration and Inflow and Sewer Deterioration Based on the Flux Stability of Sewage Markers, Environmental Sci. Tech 45: 86838690. Dusek, J., M. Dohnal, T. Vogel, and C. Ray. 2011. Field leaching of pesticides at five test sites in Hawaii: Modeling flow and transport, Pest Management Science, 67: 1571-1582. Shuai, X., J. Chen, and C. Ray. 2011. Adsorption, transport, and degradation of fipronil termiticide in three Hawaii soils, Pest Management Science, online: DOI 10.1002/ps.2320 Alavi, G., M. Chung, J. Lichwa, M. DAlessio, and C. Ray. 2011. The fate and transport of RDX, HMX, TNT, and DNT in the volcanic soils of Hawaii: A laboratory and modeling study, Journal of Hazardous Materials, 185: 1600-1604. Stone, J.J., K. R. Aurand, C.R. Dollarhide, R. Jinka, R. C. Thaler, D.E. Clay, and S.A. Clay. 2011. Determination of environmental impacts of antimicrobial usage for US Northern Great Plains swine-production facilities: a life-cycle assessment approach. Int. J. Life Cycle Assess. 16:27-39. Clay, S.A. and D.D. Malo. 2011. Herbicide sorption to soils amended with biochars produced from microwave pyrolysis. Herbicides. Vol. 3. InTech open Access book (in press) Stone, J.J., E.K. Dreis, C.D. Lupo, and S.A. Clay. 2011. Land application of tylosin and chlortetracycline swine manure: Impacts to soil nutrients and soil microbial community structure. J. Environ. Sci. Health. B46: 752-762. Stone, J.J., A.S. Oswald, C.D. Lupo, S.A. Clay, and H.V. Mott. 2011. Impact of chlortetracycline on sequencing batch reactor performance for swine manure treatment. Bioresource Technol. 102:7807-7814. Lehnert-Nelson, K., V.S. Brözel, S.A. Gibson, R. Thaler, and S.A. Clay. 2011. Influence of manure from pigs fed chlortetracycline as growth promotant on soil microbial community structure. World J. Microbiol. Biotechnol. 27:659-668. Blotevogel, J.; Borch, T. 2011. Determination of hexamethylphosphoramide and other highly polar phosphoramides in water samples using reversed-phase liquid chromatography/electrospray ionization time-of-flight mass spectrometry. Journal of Chromatography A, 1218: 6426-6432. Blotevogel, J.; Mayeno, A. N.; Sale, T. C.; Borch, T. 2011. Prediction of contaminant persistence in aqueous phase: A quantum chemical approach. Environ. Sci. Technol. 45: 2236-2242. Mawhinney, D. B.; Young, R. B.; Vanderford, B. J.; Borch, T.; Snyder, S. A. 2011. Artificial sweetener sucralose in u.S. Drinking water systems. Environ. Sci. Technol. 45: 87168722. Sivaswamy, V.; Boyanov, M. I.; Peyton, B. M.; Viamajala, S.; Gerlach, R.; Apel, W. A.; Sani, R. K.; Dohnalkova, A.; Kemner, K. M.; Borch, T. 2011. Multiple mechanisms of uranium immobilization by cellulomonas sp. Strain es6. Biotechnology and Bioengineering 108, 264-276. Yang, Y.-Y.; Pereyra, L. P.; Young, R. B.; Reardon, K. F.; Borch, T. 2011. Testosterone-mineralizing culture enriched from swine manure: Characterization of degradation pathways and microbial community composition. Environ. Sci. Technol. 45: 6879-6886. Munoz, A.M., Koskinen, W.C., Sadowsky, M.J. 2011. Biodegradation and mineralization of metolachlor by Candida xestobii. J. Agric. Food Chem. 59: 619-627. Oliveira, R.S., Alonso, D.G., Koskinen, W.C. 2011. Sorption-desorption of aminocyclopyrachlor in selected Brazilian soils. J. Agricultural Food Chem. 59:4045-4050. Sakaliene, O., Rice, P.J., Koskinen, W.C. 2011. Dissipation and transport of clopyralid in soil: Effect of application strategies. J. Agric. Food Chem. 59:7891-7895. Alonso, D.G, Koskinen, W.C., Oliveira Jr, R.S., Constantin, J., Mislankar, S. 2011. Sorption-desorption of indaziflam in tropical and glacial soils. J. Agric. Food Chem. 59 (24):1309613101. Cabrera, A., Cox, L., Spokas, K.A., Celis, R., Hermosin, M.C., Cornejo, J., Koskinen, W.C. 2011. Comparative sorption and leaching study of the herbicides fluometuron and 4-chloro-2-methylphenoxyacetic acid (MCPA) in a soil amended with biochars and other sorbents. J. Agric. Food Chem. 59 (23): 12550-12560. Pileggi, M, Veiga Pileggi, S.A., Olchanheski, L.R., Garbugio da Silva, P.A., Munoz, A.M., Koskinen, W.C., Barber, B., Sadowsky, M.J. 2012. Isolation of mesotrione-degrading bacteria from aquatic environments in Brazil. Chemosphere. (In Press) Dhakal, K. 2011. Atrazine runoff in the Blue River Basin: Geomorphology, rainfall, and agronomic practices. M.S. Thesis, University of Nebraska-Lincoln. 125 p. Dhakal, K., Bernards, M.L., Milner, M., Barnes, P.L., and Shea, P.J. 2011. Contributions of agronomic practices, precipitation patterns, and landscape vulnerability to atrazine load in the Big Blue River Basin. Weed Science Society Abstract 157: http://wssaabstracts.com/public/abstract-157.html. Hosseini, A., Milner, M., Lerch, R.N., Bernards, M.L., and Shea, P.J. 2011. Field-scale adaption of a process-based index model for landscape vulnerability to surface and ground water contamination. Soil Science Society of America Abstract 34-7: http://a-c-s.confex.com/crops/2011am/webprogram/Paper67726.html. Wei, H-R. 2011. Formation, adsorption and stability of N-nitrosoatrazine in water and soil. M.S. Thesis, University of Nebraska-Lincoln. 76 p. Wei, H-R., Rhoades, M.G., and Shea, P.J. 2011. Nitrosoatrazine formation and behavior in water and soil. American Chemical Society, 241st National Meeting, Anaheim, CA. Abstract 198. http://abstracts.acs.org/chem/241nm/program/view.php Wei, H-R., Rhoades, M.G., and Shea, P.J. 2011. Formation, adsorption, and stability of N-nitrosoatrazine in water and soil. In: It's All in the Water: Studies of Materials and Conditions in Fresh and Salt Water Bodies, M.A. Benvenuto, ed. American Chemical Society Symposium Series. Washington, DC: American Chemical Society (in press). Teixido, M., C. Hurtado, J.J. Pignatello, J.L. Beltran, M. Granados and J. Peccia. 2012. Predicting Sulfamethazine Adsorption in Biochar-Amended Soil, 2012. Environ. Sci. Technol., (under review) Schneckenburger, T. C.V. Lattao, J.J. Pignatello, G.E. Schaumann, S. Thiele-Bruhn, XY Cao, JD Mao. 2012. Preparation and Characterization of Humic acid Cross-linked with Organic Bridging Groups, Org. Geochem., pending revisions. Teixido, M., J.J. Pignatello, J.L. Beltran, M. Grenados and J. Peccia. Speciation of the Ionizable Antibiotic Sulfamethazine on Black Carbon (Biochar), 2011. Environ. Sci. Technol. 45: 1002010027. Ni, J., J. J. Pignatello, and B. Xing. 2011. Adsorption of Aromatic Carboxylate Ions to Charcoal Black Carbon is Accompanied by Proton Exchange with Water. 2011. Environ. Sci. Technol. 45: 9240-9248. Elmer, W.H. and J.J. Pignatello. 2011. Effect of Biochar Amendments on Mycorrhizal Associations and Fusarium Crown and Root Rot of Asparagus in Replant Soils, Plant Disease 95: 960-966.

Impact Statements

Since the quantum chemical methodology described herein can be applied to virtually any contaminant or reaction of interest, it is especially valuable for the prediction of persistence when slow reaction rates impede experimental investigations and appropriate QSARs are unavailable. The newly developed analytical methodology will enable scientists, regulators, and engineers to estimate the favorability of contaminant degradation at a specific field site, suitable approaches to enhance degradation, and the persistence of a contaminant and its reaction intermediates.
The results of this study confirm that sucralose will function well as an indicator compound for anthropogenic influence on source, finished drinking and distribution system (i.e., tap) water, as well as an indicator compound for the presence of other recalcitrant compounds in finished drinking water in the U.S. This will help regulators and scientists to determine if different types of water has been influenced by anthropogenic activity.
The purpose of manure treatment is to remove organic carbon, N, P, odor, chemical oxygen demand and pathogens prior to land application. In addition, the methane generated can be recovered for energy. The implications of our studies are that if chlortetracycline is present, manure may require longer processing times or an additional processing stage.
Biochar having little effect on pesticide sorption may be suitable for general application to fields, while biochar having high pesticide sorption capacity may be strategically applied to areas where pesticide sorption is highly desired (i.e. in waterways, along stream accesses, above shallow aquifers) to minimize pesticide contamination by field runoff or leaching.
Estrogens remained in the solution phase longer when liquid swine manure was present compared to calcium chloride. The effects of composting manure on total estrogenicity were similar where static composting was similar to when the compost was regularly turned. These results are significant in that the methods used to handle manure can significantly influence their longevity in the environment
The poor sorption and relative persistence of diclofenac and ibuprofen under anaerobic conditions suggest that the two chemicals may pose a high leaching risk when using recycled for irrigation or groundwater replenishment. The results suggest that MnO2 may play an important role in the environmental attenuation of BPF, and that MnO2 may be used for removing BPF in waste streams.
To our knowledge, this is the first report of the widely-dispersed P. ananatis being involved in pesticide degradation. Also, since P. ananatis rapidly degraded mesotrione, likely through cometabolic processes, this strain might be useful for bioremediation purposes.
This study has identified novel interactions of ionizable compounds on black carbon surfaces that ultimately will assist the development and application of predictive models. A consequence of proton exchange and H-bonding mechanism for study compounds (carboxylic acids, sulfonamides) is a positive shift in the pKa in the adsorbed state compared to the solution state to take advantage of the interaction.

Date of Annual Report: 04/08/2013

Report Information

Annual Meeting Dates: 01/23/2013 - 01/24/2013
Period the Report Covers: 10/01/2011 - 09/01/2012

Participants

California Riverside - University of California, Riverside, Jay Gan;Colorado - Colorado State University, Thomas Borch (accompanied by Robert Young);Connecticut - Connecticut Agricultural Experiment Station-New Haven, Joseph Pignatello;California Davis - University of California, Davis, Sanjai Parikh;Nebraska - University of Nebraska, Patrick Shea;New Mexico - New Mexico State University, Gerald Sims;Indiana - Purdue University, Linda Lee;Illinois - University of Illinois, Michael Hirschi, Lance Schideman;Missouri - University of Missouri, Keith Goyne (represented by Cammy Willett);Lee Sommers, Administrative Advisor (Colorado State University)

Brief Summary of Minutes

Joe Pignatello served as Chair of the committee and Thomas Borch served as Secretary. The Administrative Advisor, Lee Sommers, discussed the implications of just-released Report to the President on Agricultural Preparedness and the Agricultural Research Enterprise by the Presidents Council of Advisors on Science and Technology. The report deals with challenges to the nation including managing pests, increasing water efficiency, reducing the environmental footprint of agriculture, growing food in a changing climate, managing bioenergy, producing safe nutritious food, and assisting in global food security recommendations for increased funding an improved funding mechanisms for agricultural research and extension activities. The committee discussed progress in ongoing outreach efforts of W-2082, including joint grant proposals among members, upcoming and future symposia organized individually and/or jointly by members, and a planned extension publication on transport of contaminants. The committee discussed time and location of next years meeting, cognizant of members concerns about conflicts with classes and other conferences, but came to no decision. Each participant provided a research update, with discussion following each presentation.

Minutes Attachment:

Attachment

Accomplishments

See attached document in Summary of Minutes for detailed description of accomplishments.

Publications

Yang, Y.-Y., Gray, J. L., Furlong, E. T., Davis, J. G., ReVello, R. C., and Borch, T., 2012. Steroid Hormone Runoff from Agricultural Test Plots Applied with Municipal Biosolids. Environ. Sci. Technol. 46, 2746-2754. Amstaetter, K., Borch, T., and Kappler, A., 2012. Influence of humic acid imposed changes of ferrihydrite aggregation on microbial Fe(III) reduction. Geochim. Cosmochim. Acta 85, 326-341. Borch, T., Roche, N., and Johnson, T. E., 2012. Determination of contaminant levels and remediation efficacy in groundwater at a former in situ recovery uranium mine. J. Environ. Monit. 14, 1814-1823. Burgos, W. D., Borch, T., Troyer, L. D., Luan, F., Larson, L. N., Brown, J. F., Lambson, J., and Shimizu, M., 2012. Schwertmannite and Fe oxides formed by biological low-pH Fe(II) oxidation versus abiotic neutralization: Impact on trace metal sequestration. Geochim. Cosmochim. Acta 76, 29-44. Kozubal, M. A., Macur, R. E., Jay, Z. J., Beam, J. P., Malfatti, S. A., Tringe, S. G., Kocar, B. D., Borch, T., and Inskeep, W. P., 2012. Microbial iron cycling in acidic geothermal springs of Yellowstone National Park: Integrating molecular surveys, geochemical processes and isolation of novel Fe-active microorganisms. Frontiers in Microbiology 3, 1-16. Robb, T., Andrews, D., Watson, J. and Elliot, H. 2012. Humid Region Salt Accumulation in Soils at Penn State's Living Filter. SSSA Annual Meeting, Cincinnati, OH, poster presentation. Walker, C.W., J.E. Watson, C. Williams. 2012. Occurrence of Carbamazepine in Soils Under Different Land Uses Receiving Wastewater. J. Envir. Qual. 41:1263-1267. Woodward, E., Andrews, D., Williams, C. and Watson, J. 2012. Quantification of Soil Estrogen Accumulation As the Result of 25+ Years of Wastewater Irrigation. SSSA Annual Meeting, Cincinnati, OH, oral presentation. Woodward, E., Andrews, D., Williams, C. and Watson, J. 2012. Vadose Zone Transport of Estrogen Hormones at Penn State's Living Filter. AWRA Summer Specialty Conference: Contaminants of Emerging Concern in Water Resources II: Research, Engineering, and Community Action, Denver, CO, oral presentation. Woodward, E., Andrews, D., Williams, C. and Watson, J. 2012. Determination of Optimal Conditions for Sample Storage and Preparation: Enhancing Estrogen Extraction from Soils. SSSA Annual Meeting, San Antonio, TX, oral presentation. Thompson, A., and K.W. Goyne. 2012. Introduction to the sorption of chemical constituents in soils. Nature Education Knowledge 3(10):7. Unger, I.M., K.W. Goyne, A.C. Kennedy, and R. J. Kremer, J.E.T. McLain, and C.F. Williams. 2013. Antibiotic effects on microbial community characteristics in soils under conservation management practices. Soil Sci. Soc. Am. J. 77:100-112. Chu, B., K.W. Goyne, S.H. Anderson, C.H. Lin, and R.N. Lerch. In Press. Sulfamethazine sorption to soil: Vegetative management, pH, and dissolved organic matter effects. J. Environ. Qual. Chu, B., S.H. Anderson, K.W. Goyne, C.H. Lin, and R.N. Lerch. In Press. Sulfamethazine transport in agroforestry and cropland soils. Vadose Zone J. Shuai, X., J. Chen, and C. Ray. 2012. Adsorption, transport, and degradation of fipronil termiticide in three Hawaii soils, Pest Management Science, 68: 731-739. Mohanram, A., C. Ray, D.W. Metge, L.B. Barber, J.N. Ryan, and R.W. Harvey. 2012. Effect of Dissolved Organic Carbon on the Transport and Attachment Behaviors of Cryptosporidium parvum oocysts and Carboxylate-Modified Microspheres Advected through Temperate Humic and Tropical Volcanic Agricultural soil, Environmental Sci. Tech, (DOI: 10.1021/es2003342, 46(4): 2088-2094. Cutler, W.G., R.C. Brewer, A. El-Kadi, N.V. Hue, P.G. Niemeyer, J. Pierd, and C. Ray. 2013. Bioaccesible arsenic in soils of former sugar cane plantations, Island of Hawaii, Science of Total Environment, 442: 177-188. Sharma, L., J. Greskowiak, C. Ray, P. Eckert, and H. Prommer. 2012. Elucidating temperature effects on seasonal variations of biogeochemical turnover rates during riverbank filtration, J. Hydrol., 428-429: 104-115. (DOI: 10.1016/j.jhydrol.2012.01.028) Sorption Selectivity in Natural Organic Matter Studied with Nitroxyl Paramagnetic Relaxation Probes, C. Lattao, Y. Li, X. Cao, J. Mao, K. Schmidt-Rohr, M.A. Chappell, L.F. Miller, A.L. dela Cruz, and J.J. Pignatello,* Environ. Sci. Technol. 46: 1281412822 (2012). Advanced Solid-state NMR Characterization of Marine Dissolved Organic Matter Isolated Using the Coupled Reverse Osmosis/Electrodialysis Method, Jingdong Mao,* Xueqian Kong, Klaus Schmidt-Rohr, Joseph J. Pignatello, and E. Michael Perdue, Environ. Sci. Technol., 46, 58065814 (2012) doi.org/10.1021/es300521e. Impact of halide ions on natural organic matter-sensitized photolysis of 17²-Estradiol and on singlet oxygen concentration in saline waters, Janel E. Grebel, Joseph J. Pignatello, and William A. Mitch,* Environ. Sci. Technol. 46: 7128-7144 (2012). Dynamic interactions of natural organic matter and organic compounds, J.J. Pignatello*; J. Soils and Sediments, 12: 1241-1256 (2012) doi 10.1007/s11368-012-0490-4 Characterization of Wood Chars Produced at Different Temperatures using Advanced 13C Solid-state NMR Spectroscopic Techniques, Xiaoyan Cao, Joseph J. Pignatello, Yuan Li, Charisma Lattao, Mark A. Chappell, Na Chen, Lesley F. Miller, and Jingdong Mao,* Energy & Fuels. 26: 5983-5991 (2012). Characterization of oil shale, isolated kerogen, and post-pyrolysis residues using advanced 13C solid-state nuclear magnetic resonance spectroscopy, Xiaoyan Cao, Justin E. Birdwell*, Mark Chappell, Yuan Li, Joseph J. Pignatello, and Jingdong Mao, AAPG Bulletin (Amer. Assoc. Petroleum Geologists), in press (March, 2013). Preparation and Characterization of Humic acid Cross-linked with Organic Bridging Groups, T. Schneckenburger; C.V. Lattao; J.J. Pignatello*, G.E. Schaumann, S. Thiele-Bruhn; XY Cao; JD Mao, Org. Geochem., 47 (2012) 132138. Dhakal, K. 2011. Atrazine runoff in the Blue River Basin: Geomorphology, rainfall, and agronomic practices. M.S. Thesis, University of Nebraska-Lincoln 125 p. Hosseini, A. 2012. Field-scale adaption of a process-based index model for landscape vulnerability to surface and ground water contamination. M.S. Thesis, University of Nebraska-Lincoln. 110 p. Kim, S-A. J-C. Chae, S. Kamla-Kannan, K-J. Lee, Y-J. Park, P.J. Shea, W-H. Lee, H-M. Kim, and B-T. Oh. 2013. Removal of Pb(II) from aqueous solution by zeolite-supported nanoscale zero-valent iron. Chem. Eng. J. 217:54-60. Wei, H-R., M.G. Rhoades, and P.J. Shea. 2011. Formation, adsorption, and stability of N-nitrosoatrazine in water and soil. In: It's All in the Water: Studies of Materials and Conditions in Fresh and Salt Water Bodies, M.A. Benvenuto, ed. American Chemical Society Symposium Series. Washington, DC: American Chemical Society. C. Pham, L. Charlet, and G. Sposito. 2012. Does the naturally elevated sulfur content of Ulva lactuca play a role in the uptake and speciation of arsenic? Goldschmidt International Geochemistry Conference, Montréal, June 2012. Lao, W.J., and J. Gan. 2012. Enantioselective degradation of warfarin in soils. Chirality 24: 54-59. Jiang, W.Y., D. Haver, M. Rust, and J. Gan. 2012. Runoff of pyrethroid insecticides from concrete surfaces following simulated and natural rainfalls. Water Research 46: 645-652. Gan, J., S. Bondarenko, L. Oki, D. Haver, and J.X. Li. 2012. Occurrence of fipronil and its biologically active derivatives in urban residential runoff. Environmental Science & Technology 46: 1489-1495. Hu, Q.H., J.E. Moran, and J. Gan. 2012. Sorption, degradation, and transport of methyl iodide and other iodine species in geologic media. Applied Geochemistry 27: 774-781. Bondarenko, S., J. Gan, F. Ernst, R. Green, J. Baird, and M. McCullough. Leaching of pharmaceutical and personal care products (PPCPs) in turfgrass soils during recycled water irrigation. Journal of Environmental Quality 41: 1268-1274. Conkle, J.L., and J. Gan. 2012. Degradation and sorption of commonly detected PPCPs in wetland sediments under aerobic and anaerobic conditions. Journal of Soils and Sediments 12: 1164-1173. Jia, F., X.Y. Cui, W. Wang, L. Delgado-Moreno, and J. Gan. 2012. Using disposable solid phase microextraction (SPME) to determine the freely dissolved concentration of polybrominated diphenyl ethers (PBDEs) in sediments. Environmental Pollution 167: 34-40. Jiang, W.Y., and J. Gan. 2012. Importance of fine particles in pesticide runoff from concrete surfaces and its prediction. Environmental Science & Technology 46: 6028-6034. Wu, X.Q., J. Conkle, and J. Gan. 2012. Multi-residue determination of pharmaceutical and personal care products in vegetables. Journal of Chromatography A.1254: 78-86. Wright, L., D.A. Devitt, M.H. Young, J. Gan, B.J. Vanderford, S.A. Snyder, M. McCullough, and L. Dodgen. 2012. Fate and transport of 13 pharmaceutical and personal care products in a controlled and irrigated turfgrass system. Agronomy Journal 104: 1244-1254. Wang, W., L. Delgado-Moreno, J. Conkle, M. Anderson, C. Amrhein, Q.F. Ye, and J. Gan. 2012. Characterization of sediment contamination patterns by hydrophobic pesticides to preserve ecosystem functions of drainage lakes. Journal of Soils and Sediments 12:1407-1418. Lin, K.D., J.F. Ding, H.Y. Wang, X.W. Huang, and J. Gan. 2012. Geothite-mediated transformation of bisphenol A. Chemosphere 89:789-795. Cui, X.Y., P. Mayer, and J. Gan. 2013. Methods to assess bioavailability of hydrophobic organic contaminants: Principles, operations, and limitations. Environmental Pollution 172: 223-234. Cui, X.Y., and J. Gan. Comparing sorption behavior of pyrethroids between formulated and natural sediments. Environmental Toxicology & Chemistry (in press) Delgado-Moreno, L., and J. Gan. A stable isotope dilution method for measuring bioavailability of organic contaminants. Environmental Pollution (in press) Tong, Z., M. Bischoff, L. F. Nies, P. Myer B. Applegate, and R. F. Turco. 201X. Response of soil microorganisms to as-produced and functionalized single-wall carbon nanotubes (SWNTs). Environmental Sciences &Technology http://dx.doi.org/10.1021/es303251r Roskamp Jared M., Ronald F. Turco, Marianne Bischoff, and William G. Johnson. 201X. The Influence of Carrier Water pH and Hardness on Saflufenacil Efficacy and Solubility. Submitted, Weed Technology. Gall, H., S. Sassman, L.S. Lee, and C. Jafvert. 2011. Hormone Chemograph Behavior in a Tile Drained Agroecosystem Receiving Animal Wastes. Environ. Sci. Technol., 45:8755-8764. Leet, J., L.S. Lee, H. Gall, R. Goforth, S. Sassman, D. Gordon, J. Lazorchak, M. Smith, C. Jafvert, M. Sepulveda. 201X. Assessing impacts of land-applied manure from concentrated animal feeding operations on fish populations and communities. Environ. Sci. Technol., In press. Dasu, K., L.S. Lee, R.F. Turco, and L. Nies. 2012. Aerobic Biodegradation of 8:2 Fluorotelomer Stearate Monoester and 8:2 Fluorotelomer Citrate Triester in Forest Soil. Chemosphere, 10.1016/j.chemosphere.2012.11.076. Gall, H., S. Sassman*, B. Jenkinson, L.S. Lee, and C. Jafvert. 2012. Hormone Loads Exported by a Tile- Drained Agroecosystem Receiving Animal Manure Wastes. Hydrological Processes, In press. Khan, B. and L.S. Lee. 2012. Estrogens and Synthetic Androgens in Manure Slurry from Trenbolone Acetate/Estradiol Implanted Cattle and in Waste-Receiving Lagoons Used for Irrigation, Chemosphere, 89, 14431449. Card, Marcella L., Yu-Ping Chin, and Linda S. Lee. 2012. Prediction and experimental evaluation of soil sorption by natural hormones and hormone mimics. J. Food Agric. Chem., 60 (6):14801487. Dasu, K., J. Liu and L.S. Lee. 2012. Aerobic Soil Biodegradation of 8:2 Fluorotelomer Stearate Monoester Degradation. Environ. Sci. Technol., 46:3831-36, DOI: 10.1021/es203978g. Guy, A.C., T.M. DeSutter, F.X.M. Casey, R. Kolka and H. Hakk. 2012. Water quality, sediment, and soil characteristics near Fargo-Moorhead urban areas as affected by major flooding of the Red River of the North. J. Env. Qual. 41:554-563 Shrestha, S.L., F.X.M. Casey, H. Hakk, D.J. Smith and G. Padmanabhan. 2012. Fate and transformation of an estrogen conjugate and its metabolites in agricultural soils. Environ. Sci. Technol. 46:11047-11053 Shrestha, S.L., F.X.M. Casey, H. Hakk and G. Padmanabhan. 2012. A radioassay-based approach to investigate fate and transformation of conjugated and free estrogens in an agricultural soil in a laboratory setting. Environ. Engin. Sci. (Accepted) DAngelo, E., G.A. Zeigler, E. Glynn Beck, John Grove, Frank Sikora. (2012) Arsenic species in broiler (Gallus gallus domesticus) litter, soils, maize (Zea Mays L.), and groundwater from litter amended soil. Science of the Total Environment 438: 286-292. Bergeron ZL, Bingham JP (2012) Scorpion Toxins Specific for Potassium (K+) channels: A Historical Overview of Peptide Bioengineering. Toxins 4, 1082-1119. Bingham JP, Andrews EA, Kiyabu SM, Cabalteja CC (2012) Drugs from Slugs, Part II Conopeptide Bioengineering. Chemico-Biological Interactions 200 (2012) 92113. Bingham JP, Baker MR, Chun JB. (2012) Analysis of a cone snail's killer cocktail - The milked venom of Conus geographus. Toxicon. Nov;60(6):1166-70. Chun JB, Baker MR, Kim D H, Leroy M, Toribo P, Bingham JP (2012) Cone snail milked venom dynamics a quantitative study of Conus purpurascens. Toxicon. 60(1):83.

Impact Statements

These new discoveries will enable scientists, waste managers, regulators, and engineers to estimate the runoff potential of steroid hormones from biosolids amended soils under various conditions (e.g., just before a heavy rainfall) and the likelihood for photodegradation of androgens in surface waters. The information can also be used to assess the potential for endocrine disruption by testosterone and androstenedione photodegradation products.
A community project in Pittsburgh was implemented which combined curbing changes with landscape plantings and porous sidewalk pavement. Sample results demonstrated that these practice changes significantly reduced runoff of sediments, E. Coli, and heavy metals into a storm sewer, thus reducing the areas contribution to surface water contamination and sewer flows.
Our results indicate that only highly surfaceous, carbonaceous biochars would be useful for stabilizing soil contaminated with compounds such as sulfamethazine. They also suggest that weathering may attenuate the contribution of native (environmental) black carbon to sorption of such compounds in soils and sediments.
By investigating the chemical forms of As found in algae under controlled conditions, we were able to determine the effects of phosphate nutrient status on the uptake and speciation of As in the proposed bioindicator alga, Ulva lactuca. We are continuing this research to determine the potential of Ulva lactuca in biomonitoring and phytoremediation scenarios where agricultural inputs of As may impact coastal environments.
The results of this study indicate that we can bioengineer new peptide toxins that target specific organisms. Here the development of new pesticides requires intense investigation to ensure minimum residue footprint in the environment. Their use will increase food safety; limiting crop damage and decreasing the risk to humans of molluscan borne diseases.